Search results for: cement hydration

Authors: Rym Sassi, Franck Fayon, Mohend Chaouche, Emmanuel Veron, Valerie Montouillout

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The chemical phenomena occurring during cement hydration are complex and interdependent, and even after almost two centuries of studies, they are still difficult to solve for complex mixtures combining different hydraulic binders. Powder-XRD has been widely used for characterizing the crystalline phases in both anhydrous and hydrated cement, but only limited information is obtained in the case of strongly disordered and amorphous phases. In contrast, local spectroscopies like solid-state NMR can provide a quantitative description of noncrystalline phases. In this work, the structural modifications occurring during hydration of a fast-setting ternary binder based on white Portland cement, white calcium aluminate cement, and calcium sulfate were investigated using advanced solid-state NMR methods. We particularly focused on the early stage of the hydration up to 28 days, working with samples whose hydration was controlled and stopped. ²⁷Al MQ-MAS as well as {¹H}-²⁷Al and {¹H}-²⁹Si Cross- Polarization MAS NMR techniques were combined to distinguish all of the aluminum and silicon species formed during the hydration. The NMR quantification of the different phases was conducted in parallel with the XRD analyses. The consumption of initial products, as well as the precipitation of hydraulic phases (ettringite, monosulfate, strätlingite, CSH, and CASH), were unambiguously quantified. Finally, the drawing of the consumption and formation of phases was correlated with mechanical strength measurements.

Keywords: cement, hydration, hydrates structure, mechanical strength, NMR

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Authors: S. Al-Fadala, J. Chakkamalayath, S. Al-Bahar, A. Al-Aibani, S. Ahmed

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Globally, the use of pozzolan in blended cement is gaining great interest due to the desirable effect of pozzolan from the environmental and energy conservation standpoint and the technical benefits they provide to the performance of cement. The deterioration of concrete structures in the marine environment and extreme climates demand the use of pozzolana cement in concrete construction in the Gulf region. Also, natural sources of cement clinker materials are limited in the Gulf region, and cement industry imports the raw materials for the production of Portland cement, resulting in an increase in the greenhouse gas effect due to the CO₂ emissions generated from transportation. Even though the Gulf region has vast deposits of natural pozzolana, it is not explored properly for the production of high performance concrete. Hence, an optimum use of regionally available natural pozzolana for the production of blended cement can result in sustainable construction. This paper investigates the effect of incorporating natural pozzolan sourced from the Gulf region on the performance of blended cement in terms of heat evolution and strength development. For this purpose, a locally produced Ordinary Portland Cement (OPC) and pozzolan-incorporated blended cements containing different amounts of natural pozzolan (volcanic ash) were prepared on laboratory scale. The strength development and heat evolution were measured and quantified. Promising results of strength development were obtained for blends with the percentages of Volcanic Ash (VA) replacement varying from 10 to 30%. Results showed that the heat of hydration decreased with increase in percentage of replacement of OPC with VA, indicating increased retardation in hydration due to the addition of VA. This property could be used in mass concreting in which a reduction in heat of hydration is required to reduce cracking in concrete, especially in hot weather concreting.

Keywords: blended cement, hot weather, hydration, volcanic ash

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Authors: Anton Trník, Lenka Scheinherrová, Robert Černý

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Silica fume is a by-product of the ferro-silicon and silicon metal industries. It is mainly in the form of amorphous silica. Silica fume belongs to pozzolanic active materials which can be used in concrete to improve its final properties. In this paper, the influence of silica fume on hydration of cement pastes is studied using differential scanning calorimetry (DSC) and thermogravimetry (TG) at various curing times (2, 7, 28, and 90 days) in the temperature range from 25 to 1000 °C in an argon atmosphere. Samples are prepared from Portland cement CEM I 42.5 R which is partially replaced with the silica fume of 4, 8, and 12 wt.%. The water/binder ratio is chosen as 0.5. It is identified and described the liberation of physically bound water, calcium–silicate–hydrates dehydration, portlandite and calcite decomposition in studied samples. Also, it is found out that an exothermic peak at 950 °C is observed without a significant mass change for samples with 12 wt.% of silica fume after two days of hydration. This peak is probably caused by the pozzolanic reaction between silica fume and Portland cement. Its size corresponds to the degree of crystallization between Ca and Si. The portlandite content is lower for the samples with a higher amount of silica fume.

Keywords: differential scanning calorimetry, hydration, silica fume, thermogravimetry

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Authors: Karine Pimenta Teixeira, Jessica Flores, Isadora PerdigãO Rocha, Leticia De Sá Carneiro, Mahsa Kamali, Ali Ghahremaninezhad

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The advent of nanotechnology has enabled innovative solutions towards improving the behavior of infrastructure materials. Nanomaterials have the potential to revolutionize the construction industry by improving the performance and durability of construction materials, as well as imparting new functionalities to these materials. Due to variability in the environmental temperature during mixing and curing of cementitious materials in practice, it is important to understand how curing temperature influences the behavior of cementitious materials. In addition, high temperature curing is relevant in applications such as oil well cement and precast industry. Knowledge of the influence of temperature on the performance of cementitious materials modified with nanoparticles is important in the nanoengineering of cementitious materials in applications such as oil well cement and precast industry. This presentation aims to investigate the influence of temperature on the hydration, mechanical properties and durability of cementitious materials modified with TiO2 nanoparticles. It was found that temperature improved the early hydration. The cement pastes cured at high temperatures showed an increase in the compressive strength at early age but the strength gain decreased at late ages. The electrical resistivity of the cement pastes cured at high temperatures was shown to decrease more noticeably at late ages compared to that of the room temperature cured cement paste. SEM examination indicated that hydration product was more uniformly distributed in the microstructure of the cement paste cured at room temperature compared to the cement pastes cured at high temperature.

Keywords: cement paste, nanoparticles, temperature, hydration

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Authors: Yaniv Knop, Alva Peled

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Over the past few years there has been a growing interest in the development of Portland Composite Cement, by partial replacement of the clinker with mineral additives. The motivations to reduce the clinker content are threefold: (1) Ecological - due to lower emission of CO2 to the atmosphere; (2) Economical - due to cost reduction; and (3) Scientific\Technology – improvement of performances. Among the mineral additives being used and investigated, limestone is one of the most attractive, as it is considered natural, available, and with low cost. The goal of the research is to develop green cement, by partial replacement of the clinker with limestone powder while improving the performances of the cement paste. This work studied blended cements with three limestone powder particle diameters: smaller than, larger than, and similarly sized to the clinker particle. Blended cement with limestone consisting of one particle size distribution and limestone consisting of a combination of several particle sizes were studied and compared in terms of hydration rate, hydration degree, and water demand to achieve normal consistency. The performances of these systems were also compared with that of the original cement (without added limestone). It was found that the ability to replace an active material with an inert additive, while achieving improved performances, can be obtained by increasing the packing density of the cement-based particles. This may be achieved by replacing the clinker with limestone powders having a combination of several different particle size distributions. Mathematical and physical models were developed to simulate the setting history from initial to final setting time and to predict the packing density of blended cement with limestone having different sizes and various contents. Besides the effect of limestone, as inert additive, on the packing density of the blended cement, the influence of the limestone particle size on three different chemical reactions were studied; hydration of the cement, carbonation of the calcium hydroxide and the reactivity of the limestone with the hydration reaction products. The main results and developments will be presented.

Keywords: packing density, hydration degree, limestone, blended cement

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Authors: Seok Woo Chang

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Aim: The objective of this study was to compare and evaluate the hydration products of commercial and experimental calcium silicate cement. Materials and Methods: The commercial calcium silicate cement (ProRoot MTA, Dentsply) and experimental calcium silicate cement (n=10) were mixed with distilled water (water/powder ratio = 20 w/w) and stirred at room temperature for 10 hours. These mixtures were dispersed on wafer and dried for 12 hours at room temperature. Thereafter, the dried specimens were examined with Scanning Electron Microscope (SEM). Electron Dispersive Spectrometry (EDS) was also carried out. Results: The commercial calcium silicate cement (ProRoot MTA) and experimental calcium silicate cement both showed precipitation of rod-like and globule-like crystals. Based on EDS analysis, these precipitates were supposed to be calcium hydroxide or calcium silicate hydrates. The degree of formation of these precipitates was higher in commercial MTA. Conclusions: Based on the results, both commercial and experimental calcium silicate cement had ability to produce calcium hydroxide or calcium silicate hydrate precipitates.

Keywords: calcium silicate cement, ProRoot MTA, precipitation, calcium hydroxide, calcium silicate hydrate

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Authors: Bertilia L. Bartley, Ledjane S. Barreto

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As a preliminary investigation on the control of microcracking in composite cement pastes, this study explores and compares the compatibility of Tetraethyl Orthosilicate (TEOS), Ethylene Glycol (EG) and Silicone Resin (SIL) in cement pastes cured at high temperature. Pastes were prepared by incorporating ordinary Portland cement (OPC) into an additive solution, using a solution/cement ratio of 0.45. Specimens were molded for 24h at 21 ± 2°C, then cured in deionized water for another 24h at 74 ± 1°C. TEOS and EG influence on fresh paste properties were similar to the reference OPC paste yet disintegration was observed in EG and SIL specimens after the first 12h of curing. X-Ray Diffraction analysis (XRD) coupled with thermogravimetric analysis (TGA/DTG) verified that SIL addition impedes portlandite formation significantly. Backscatter Scanning Electron Microscopy (SEM) techniques were therefore performed on selected areas of each sample to investigate the morphology of the hydration products detected. Various morphologies of portlandite crystals were observed in pastes with EG and TEOS addition, as well as dense morphologies of calcium silicate hydrate (C-S-H) gel and fibers, and ettringite needles. However, the formation of portlandite aggregate and clusters of C-S-H was highly favored by TEOS addition. Furthermore, the microstructural details of composite pastes were clearly visible at low magnifications i.e. 500x, as compared to the OPC paste. The results demonstrate accelerated hydration within composite pastes, a uniform distribution of hydration products, as well as an adhesive interaction with the products and polymer additive. Overall, TEOS demonstrated the most favorable influence, which indicates the potential of TEOS as a compatible polymer additive within the cement system at high temperature.

Keywords: accelerated curing, cement/polymer composite, hydration, microstructural properties, morphology, portlandite, scanning electron microscopy (sem)

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Authors: A.M. Kaja, Q. Yu, H.J.H Brouwers

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An increased functionality of concrete towards higher eco-efficiency is nowadays of great importance due to the decreasing air quality in urban areas. Surface modifications of concrete walls and roads, as a coating or an intermixing of the surface layer with TiO₂, provide an opportunity to improve the air quality by reducing NOx via photocatalytic phenomena. Nevertheless, there are still concerns regarding the cost-efficiency as well as the toxicity of intermediate products which can be produced during the photocatalysis, limiting a widespread adoption of these materials. This study addresses the problem of the selectivity of cement mortars towards nitrate in terms of microstructural characteristics and hydration products. The ability of cement mortars matrix intermixed with commercial TiO₂ and TiO₂-SiO₂ composite to abate NO₂ is investigated. The influence of hydration products formed under the carbonation facilitating conditions is discussed and solutions how to optimize the mix design are proposed. The incorporation of the TiO₂-SiO₂ composite into cement mortar is found to increase the nitrate selectivity index.

Keywords: cement matrix, NO₂ abatement, photocatalysis, TiO₂-SiO₂ composite

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Authors: K. Arroudj, M. Lanez, M. N. Oudjit

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The introduction of siliceous mineral additions in cement production allows, in addition to the ecological and economic gain, improvement of concrete performance. This improvement is mainly due to the fixing of Portlandite, released during the hydration of cement, by fine siliceous, forming denser calcium silicate hydrates and therefore a more compact cementitious matrix. This research is part of the valuation of the Dune Sand (DS) in the cement industry in Algeria. The high silica content of DS motivated us to study its effect, at ground state, on the properties of mortars in fresh and hardened state. For this purpose, cement pastes and mortars based on ground dune sand (fine quartz) has been analyzed with a replacement to cement of 15%, 20% and 25%. This substitution has reduced the amount of heat of hydration and avoids any risk of initial cracking. In addition, the grinding of the dune sand provides amorphous thin populations adsorbed at the surface of the crystal particles of quartz. Which gives to ground quartz pozzolanic character. This character results an improvement of mechanical strength of mortar (66 MPa in the presence of 25% of ground quartz).

Keywords: mineralogical structure, pozzolanic reactivity, Quartz, mechanical strength

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Authors: Marine Regnier, Pascal Bost, Matthieu Horgnies

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Some of the problems to be solved for the concrete industry are linked to the use of low-reactivity cement, the hardening of concrete under cold-weather and the manufacture of pre-casted concrete without costly heating step. The development of these applications needs to accelerate the hydration kinetics, in order to decrease the setting time and to obtain significant compressive strengths as soon as possible. The mechanisms enhancing the hydration kinetics of alite or Portland cement (e.g. the creation of nucleation sites) were already studied in literature (e.g. by using distinct additions such as titanium dioxide nanoparticles, calcium carbonate fillers, water-soluble polymers, C-S-H, etc.). However, the goal of this study was to establish a clear ranking of the efficiency of several types of additions by using a robust and reproducible methodology based on isothermal calorimetry (performed at 20°C). The cement was a CEM I 52.5N PM-ES (Blaine fineness of 455 m²/kg). To ensure the reproducibility of the experiments and avoid any decrease of the reactivity before use, the cement was stored in waterproof and sealed bags to avoid any contact with moisture and carbon dioxide. The experiments were performed on Portland cement pastes by using a water-to-cement ratio of 0.45, and incorporating different compounds (industrially available or laboratory-synthesized) that were selected according to their main composition and their specific surface area (SSA, calculated using the Brunauer-Emmett-Teller (BET) model and nitrogen adsorption isotherms performed at 77K). The intrinsic effects of (i) dry powders (e.g. fumed silica, activated charcoal, nano-precipitates of calcium carbonate, afwillite germs, nanoparticles of iron and iron oxides , etc.), and (ii) aqueous solutions (e.g. containing calcium chloride, hydrated Portland cement or Master X-SEED 100, etc.) were investigated. The influence of the amount of addition, calculated relatively to the dry extract of each addition compared to cement (and by conserving the same water-to-cement ratio) was also studied. The results demonstrated that the X-SEED®, the hydrated calcium nitrate, the calcium chloride (and, at a minor level, a solution of hydrated Portland cement) were able to accelerate the hydration kinetics of Portland cement, even at low concentration (e.g. 1%wt. of dry extract compared to cement). By using higher rates of additions, the fumed silica, the precipitated calcium carbonate and the titanium dioxide can also accelerate the hydration. In the case of the nano-precipitates of calcium carbonate, a correlation was established between the SSA and the accelerating effect. On the contrary, the nanoparticles of iron or iron oxides, the activated charcoal and the dried crystallised hydrates did not show any accelerating effect. Future experiments will be scheduled to establish the ranking of these additions, in terms of accelerating effect, by using low-reactivity cements and other water to cement ratios.

Keywords: acceleration, hydration kinetics, isothermal calorimetry, Portland cement

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Authors: Geta Bekalu Belayneh, Solmoi Park

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This study examines the role of slag in the process of hydration and carbonation of carbonation-cured slag cement. Carbonation-cured slag-blended cement paste samples were prepared with varying slag percentages of 0%, 10%, 30%, and 50%. The curing process lasted for a maximum of 28 days. The findings demonstrated that the carbonation depth increased as the curing period was extended, and a larger slag percentage promoted a more extensive penetration of carbonation. The degree of belite reaction was greatly enhanced in the slag-blended cement, resulting in an increased ability to bind CO₂ in the blended cement. These findings enhance comprehension of the behaviour of blended cement produced through carbonation-curing, facilitating the advancement of more environmentally friendly and long-lasting concrete constructions.

Keywords: carbonation curing, blast furnace slag, characterization, Portland cement

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Authors: Andrea Cretu, Calin Cadar, Maria Miclaus, Lucian Barbu-Tudoran, Siegfried Stapf, Ioan Ardelean

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Additives and mineral admixtures have become an integral part of cement-based materials. It is common practice to add silica fume to cement based mixes in order to produce high-performance concrete. There is still a lack of scientific understanding regarding the effects that silica fume has on the microstructure of hydrated cement paste. The aim of the current study is to develop high-performance materials with low permeability and high resistance to flexural stress using silica fume and an organosilane. Organosilane bonds with cement grains and silica fume, influencing both the workability and the final properties of the mix, especially the pore size distributions and pore connectivity. Silica fume is a known pozzolanic agent which reacts with the calcium hydroxide in hydrated cement paste, producing more C-S-H and improving the mechanical properties of the mix. It is believed that particles of silica fume act as capillary pore fillers and nucleation centers for C-S-H and other hydration products. In order to be able to design cement-based materials with added silica fume and organosilane, it is necessary first to understand the formation of the porous network during hydration and to observe the distribution of pores and their connectivity. Nuclear magnetic resonance (NMR) methods in low-fields are non-destructive and allow the study of cement-based materials from the standpoint of their porous structure. Other methods, such as XRD and SEM-EDS, help create a comprehensive picture of the samples, along with the classic mechanical tests (compressive and flexural strength measurements). The transverse relaxation time (T₂) was measured during the hydration of 16 samples prepared with two water/cement ratios (0.3 and 0.4) and different concentrations or organosilane (APTES, up to 2% by mass of cement) and silica fume (up to 6%). After their hydration, the pore size distribution was assessed using the same NMR approach on the samples filled with cyclohexane. The SEM-EDS and XRD measurements were applied on pieces and powders prepared from the samples that were used in mechanical testing, which were kept under water for 28 days. Adding silica fume does not influence the hydration dynamics of cement paste, while the addition of organosilane extends the dormancy stage up to 10 hours. The size distribution of the capillary pores is not influenced by the addition of silica fume or organosilane, while the connectivity of capillary pores is decreased only when there is organosilane in the mix. No filling effect is observed even at the highest concentration of silica fume. There is an apparent increase in flexural strength of samples prepared only with silica fume and a decrease for those prepared with organosilane, with a few exceptions. XRD reveals that the pozzolanic reactivity of silica fume can only be observed when there is no organosilane present and the SEM-EDS method reveals the pore distribution, as well as hydration products and the presence or absence of calcium hydroxide. The current work was funded by the Romanian National Authority for Scientific Research, CNCS – UEFISCDI, through project PN-III-P2-2.1-PED-2016-0719.

Keywords: cement hydration, concrete admixtures, NMR, organosilane, porosity, silica fume

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Authors: Mokhtar Nikgoo

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Definition of Concrete and Concreting: Concrete (in French: Béton) in a broad sense is any substance or combination that consists of a sticky substance with the property of cementation. In general, concrete refers to concrete made by Portland cement, which is produced by mixing fine and coarse aggregates, Portland cement and water. After enough time, this mixture turns into a stone-like substance. During the hardening or processing of the concrete, cement is chemically combined with water to form strong crystals that bind the aggregates together, a process called hydration. During this process, significant heat is released called hydration heat. Additionally, concrete shrinks slightly, especially as excess water evaporates, a phenomenon known as drying shrinkage. The process of hardening and the gradual increase in concrete strength that occurs with it does not end suddenly unless it is artificially interrupted. Instead, it decreases more over long periods of time, although, in practical applications, concrete is usually set after 28 days and is considered at full design strength. Concrete may be made from different types of cement as well as pozzolans, furnace slag, additives, additives, polymers, fibers, etc. It may also be used in the way it is made, heating, water vapor, autoclave, vacuum, hydraulic pressures and various condensers.

Keywords: concrete, RCC, batching, cement, Pozzolan, mixing plan

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Authors: M. Boháč, R. Novotný, F. Frajkorová, R. S. Yadav, T. Opravil, M. Palou

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Properties of Portland cement mixtures with various fractions of metakaolin were studied. 10 % of Portland cement CEM I 42.5 R was replaced by different fractions of high reactivity metakaolin with defined chemical and mineralogical properties. Various fractions of metakaolin were prepared by jet mill classifying system. There is a clear trend between fineness of metakaolin and hydration heat development. Due to metakaolin presence in mixtures the compressive strength development of mortars is rather slower for coarser fractions but 28-day flexural strengths are improved for all fractions of metakaoline used in mixtures compared to reference sample of pure Portland cement. Yield point, plastic viscosity and adhesion of fresh pastes are considerably influenced by fineness of metakaolin used in cement pastes.

Keywords: calorimetry, cement, metakaolin fineness, rheology, strength

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Authors: M. Tazky, R. Hela, P. Novosad, L. Osuska

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This paper deals with the possibility of safe incorporation fluidised bed combustion fly ash (waste material) into cement matrix together with next commonly used secondary raw material, which is high-temperature fly ash. Both of these materials have a very high pozzolanic ability, and the right combination could bring important improvements in both the physico-mechanical properties and the better durability of a cement composite. This paper tries to determine the correct methodology for designing green concrete by using modern methods measuring rheology of fresh concrete and following hydration processes. The use of fluidised bed combustion fly ash in cement composite production as an admixture is not currently common, but there are some real possibilities for its potential. The most striking negative aspect is its chemical composition which supports the development of new product formation, influencing the durability of the composite. Another disadvantage is the morphology of grains, which have a negative effect on consistency. This raises the question of how this waste can be used in concrete production to emphasize its positive properties and eliminate negatives. The focal point of the experiment carried out on cement pastes was particularly on the progress of hydration processes, aiming for the possible acceleration of pozzolanic reactions of both types of fly ash.

Keywords: high temperature fly ash, fluidized bed combustion fly ash, pozzolan, CaO (calcium oxide), rheology

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Authors: E. Poupelloz, S. Gauffinet

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Ettringite Ca₆Al₂(SO₄)₃(OH)₁₂26H₂O is one of the major hydrates formed during cement hydration. Ettringite forms in Portland cement from the reaction between tricalcium aluminate Ca₃Al₂O₆ and calcium sulfate. Ettringite is also present in calcium sulfoaluminate cement in which it is the major hydrate, formed by the reaction between yeelimite Ca₄(AlO₂)₆SO₄ and calcium sulfate. About the formation of ettringite, numerous results are available in the literature even if some issues are still under discussion. However, almost all published work about ettringite was done on cementitious systems. Yet in cement, hydration reactions are very complex, the result of dissolution-precipitation processes and are submitted to various interactions. Understanding the formation process of a phase alone, here ettringite, is the first step to later understand the much more complex reactions happening in cement. This study is crucial for the comprehension of early cement hydration and physical behavior. Indeed formation of hydrates, in particular, ettringite, will have an influence on the rheological properties of the cement paste and on the need for admixtures. To make progress toward the understanding of existing phenomena, a specific study of nucleation and growth processes of ettringite was conducted. First ettringite nucleation was studied in ionic aqueous solutions, with controlled but different experimental conditions, as different supersaturation degrees (β), different pH or presence of exogenous ions. Through induction time measurements, interfacial ettringite crystals solution energies (γ) were determined. Growth of ettringite in supersaturated solutions was also studied through chain crystallization reactions. Specific BET surface area measurements and Scanning Electron Microscopy observations seemed to prove that growth process is favored over the nucleation process when ettringite crystals are initially present in a solution with a low supersaturation degree. The influence of stirring on ettringite formation was also investigated. Observation was made that intensity and nature of stirring have a high influence on the size of ettringite needles formed. Needle sizes vary from less than 10µm long depending on the stirring to almost 100µm long without any stirring. During all previously mentioned experiments, initially present ions are consumed to form ettringite in such a way that the supersaturation degree with regard to ettringite is decreasing over time. To avoid this phenomenon a device compensating the drop of ion concentrations by adding some more solutions, and therefore always have constant ionic concentrations, was used. This constant β recreates the conditions of the beginning of cement paste hydration, when the dissolution of solid reagents compensates the consumption of ions to form hydrates. This device allowed the determination of the ettringite precipitation rate as a function of the supersaturation degree β. Taking samples at different time during ettringite precipitation and doing BET measurements allowed the determination of the interfacial growth rate of ettringite in m²/s. This work will lead to a better understanding and control of ettringite formation alone and thus during cements hydration. This study will also ultimately define the impact of ettringite formation process on the rheology of cement pastes at early age, which is a crucial parameter from a practical point of view.

Keywords: cement hydration, ettringite, morphology of crystals, nucleation-growth process

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Authors: Aliakbar Sayadi, Thomas Neitzert, Charles Clifton

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The hydration process of a green concrete with differences on fly ash and the poly-lactic acid ratio was investigated using electrical resistivity measurement. The results show that the hydration process of proposed concrete was significantly different with concrete containing petroleum aggregate. Moreover, a microstructure analysis corresponding to each hydration stage is conducted with scanning microscope for ploy-lactic acid and expanded polystyrene concrete. In addition, specific equations using the variables of this study were developed to understand and predict the relationship between setting time and resistivity development of proposed concrete containing eco-friendly aggregate.

Keywords: green concrete, SEM, hydration mechanism, eco-friendly aggregate

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Authors: M.S. El-Feky, Passant Youssef, Mohamed I. Serag

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nowadays, nanotechnology is the main trend of research in different areas due to the new potential of using nanometer materials sized less than 100nm. Nanomaterials are needed in cement composites to act as bridging for Nano and micro-cracks to increase tensile strength, reduce the permeability of gases and water in concrete to solve corrosion problem, react with excess Calcium Hydroxide, produce additional C-S-H, act as filler materials to densify the cement matrix and increase its mechanical properties. The present study focuses on the effectiveness of super-plasticizers and ultrasonic processing on the dispersion of Carbon Nanotube at first in water and then in cement composites in combination with Nano silica to enhance the mechanical properties of cement composites. A qualitative analysis using a compressive strength test is conducted with a view to investigate the influence of different dispersion techniques on the mechanical properties of cement composites containing Carbon Nanotube (CNT) and Nano Silica (NS) particles with different percentages. In addition, micro-structural analysis was carried out to understand the surface morphology and microstructure of cement composites with different dosages of NS addition. The investigational study results showed that the combination of NS with a low amount of CNT had a positive effect on the hydration reaction; on the other hand, the combination of CNT and a high amount of NS had a negative effect on the hydration reaction. The compressive strength can be improved by optimum combination 0.02% CNT and 1% NS with gain in strength by 72% and 35% after 7 and 28 days compared to control samples; these results were with an agreement with the morphology structure of composites using microstructure analysis.

Keywords: nano silica, dispersion, sonication, carbon nano tubes

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Authors: Ram V. Mohan, John Rivas-Murillo, Ahmed Mohamed, Wayne D. Hodo

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Cementitious materials, an excellent example of highly complex, heterogeneous material systems, are cement-based systems that include cement paste, mortar, and concrete that are heavily used in civil infrastructure; though commonly used are one of the most complex in terms of the material morphology and structure than most materials, for example, crystalline metals. Processes and features occurring at the nanometer sized morphological structures affect the performance, deformation/failure behavior at larger length scales. In addition, cementitious materials undergo chemical and morphological changes gaining strength during the transient hydration process. Hydration in cement is a very complex process creating complex microstructures and the associated molecular structures that vary with hydration. A fundamental understanding can be gained through multi-scale level modeling for the behavior and properties of cementitious materials starting from the material chemistry level atomistic scale to further explore their role and the manifested effects at larger length and engineering scales. This predictive modeling enables the understanding, and studying the influence of material chemistry level changes and nanomaterial additives on the expected resultant material characteristics and deformation behavior. Atomistic-molecular dynamic level modeling is required to couple material science to engineering mechanics. Starting at the molecular level a comprehensive description of the material’s chemistry is required to understand the fundamental properties that govern behavior occurring across each relevant length scale. Material chemistry level models and molecular dynamics modeling and simulations are employed in our work to describe the molecular-level chemistry features of calcium-silicate-hydrate (CSH), one of the key hydrated constituents of cement paste, their associated deformation and failure. The molecular level atomic structure for CSH can be represented by Jennite mineral structure. Jennite has been widely accepted by researchers and is typically used to represent the molecular structure of the CSH gel formed during the hydration of cement clinkers. This paper will focus on our recent work on the shear and compressive deformation and failure behavior of CSH represented by Jennite mineral structure that has been widely accepted by researchers and is typically used to represent the molecular structure of CSH formed during the hydration of cement clinkers. The deformation and failure behavior under shear and compression loading deformation in traditional hydrated CSH; effect of material chemistry changes on the predicted stress-strain behavior, transition from linear to non-linear behavior and identify the on-set of failure based on material chemistry structures of CSH Jennite and changes in its chemistry structure will be discussed.

Keywords: cementitious materials, deformation, failure, material chemistry modeling

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Authors: Maryam Ghareh Chaei, Masuzyo Chilwesa, Ali Akbarnezhad, Arnaud Castel, Redmond Lloyd, Stephen Foster

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Cement hydration is an exothermic chemical reaction generally leading to a rise in concrete’s temperature. This internal heating of concrete may, in turn, lead to a temperature difference between the hotter interior and the cooler exterior of concrete and thus differential thermal stresses in early ages which could be particularly significant in mass concrete. Such differential thermal stresses result in early age thermal cracking of concrete when exceeding the concrete’s tensile strength. The extent of temperature rise and thus early age differential thermal stresses is generally a function of hydration heat intensity, thermal properties of concrete and size of the concrete element. Both hydration heat intensity and thermal properties of concrete may vary considerably with variations in the type cementitious materials and other constituents. With this in mind, partial replacement of cement with supplementary cementitious materials including fly ash and ground granulated blast furnace slag has been investigated widely as an effective strategy to moderate the heat generation rate and thus reduce the risk of early age thermal cracking of concrete. However, there is currently a lack of adequate literature on effect of partial replacement of cement with fly ash and/or ground granulated blast furnace slag on the thermal properties of concrete. This paper presents the results of an experimental conducted to evaluate the effect of addition of varying percentages of fly ash (up to 60%) and ground granulated blast furnace slag (up to 50%) on the heat capacity and thermal conductivity of early age cement paste. The water to cementitious materials ratio is kept 0.45 for all the paste samples. The results of the experimental studies were used in a numerical analysis performed using Comsol Multiphysics to highlight the effects of variations in the thermal properties of concrete, due to variations in the type of aggregate and content of supplemenraty cementitious materials, on the risk of early age cracking of a concrete raft.

Keywords: thermal diffusivity, early age thermal cracking, concrete, supplementary cementitious materials

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Authors: M. Murmu, Govardhan, J. Satya Eswari

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Concrete is the most common and widely used building material. Concrete is basically made of aggregates, both fine and coarse, glued by a cement paste which is made of cement and water. Each one of these constituents of concrete has a negative environmental impact and gives rise to different sustainability issues. The current concrete construction practice is unsustainable because, not only it consumes enormous quantities of stones, sand, and drinking water, but also one billion tons a year of cement, which is not an environment friendly material. Preventing the reduction of natural resources and enhancing the usage of waste materials has become a challenge to the scientist and engineers. A number of studies have been conducted concerning the protection of natural resources, prevention of environmental pollution and contribution to the economy by using this waste material. This paper outlines the influence of Ground Granulated Blast furnace Slag (GGBS) as partial replacement of fine aggregate on mechanical properties of concrete. The strength of concrete is determined having OPC binder, replaced the fine aggregate with15%, 30%, 45% respectively. For this purpose, characteristics concrete mix of M25 with partial replacement of cement with GGBS is used and the strength of concrete cubes and cylinder have determined. The strength of concrete specimens has been compared with the reference specimen. Also X-ray diffraction (XRD) and scanning electron microscope (SEM) tests have been performed to examine the hydration products and the microstructure of the tested specimens. A correlation has been established between the developmental strength concrete with and without GGBS through analysis of hydration products and the microstructure.

Keywords: GGBS, sand, concrete, workability

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Authors: Aliyu Usman, Muhaammed Bello Ibrahim, Yusuf D. Amartey, Jibrin M. Kaura

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This research is aimed at investigating the effect of using amorphous silica ash (ASA) obtained from rice husk as a partial replacement of ordinary Portland cement (OPC) on the mechanical and microstructure properties of cement paste and mortar. ASA was used in partial replacement of ordinary Portland cement in the following percentages 3 percent, 5 percent, 8 percent and 10 percent. These partial replacements were used to produce Cement-ASA paste and Cement-ASA mortar. ASA was found to contain all the major chemical compounds found in cement with the exception of alumina, which are SiO2 (91.5%), CaO (2.84%), Fe2O3 (1.96%), and loss on ignition (LOI) was found to be 9.18%. It also contains other minor oxides found in cement. Consistency of Cement-ASA paste was found to increase with increase in ASA replacement. Likewise, the setting time and soundness of the Cement-ASA paste also increases with increase in ASA replacements. The test on hardened mortar were destructive in nature which include flexural strength test on prismatic beam (40mm x 40mm x 160mm) at 2, 7, 14 and 28 days curing and compressive strength test on the cube size (40mm x 40mm, by using the auxiliary steel platens) at 2,7,14 and 28 days curing. The Cement-ASA mortar flexural and compressive strengths were found to be increasing with curing time and decreases with cement replacement by ASA. It was observed that 5 percent replacement of cement with ASA attained the highest strength for all the curing ages and all the percentage replacements attained the targeted compressive strength of 6N/mm2 for 28 days. There is an increase in the drying shrinkage of Cement-ASA mortar with curing time, it was also observed that the drying shrinkages for all the curing ages were greater than the control specimen all of which were greater than the code recommendation of less than 0.03%. The scanning electron microscope (SEM) was used to study the Cement-ASA mortar microstructure and to also look for hydration product and morphology.

Keywords: amorphous silica ash, cement mortar, cement paste, scanning electron microscope

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Authors: Laura Dembovska, Diana Bajare, Ina Pundiene, Daira Erdmane

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The aim of this research is to estimate effect of pozzolanic substitutes and their combination on the hydration heat and final strength of high performance concrete. Ternary cementitious systems with different ratios of ordinary Portland cement, silica fume and calcined clay were investigated. Local illite clay was calcined at temperature 700oC in rotary furnace for 20 min. It has been well recognized that the use of pozzolanic materials such as silica fume or calcined clay are recommended for high performance concrete for reduction of porosity, increasing density and as a consequence raising the chemical durability of the concrete. It has been found, that silica fume has a superior influence on the strength development of concrete, but calcined clay increase density and decrease size of dominating pores. Additionally it was found that the rates of pozzolanic reaction and calcium hydroxide consumption in the silica fume-blended cement pastes are higher than in the illite clay-blended cement pastes, it strongly depends from the amount of pozzolanic substitutes which are used. If the pozzolanic reaction is dominating then amount of Ca(OH)2 is decreasing. The identity and the amount of the phases present were determined from the thermal analysis (DTA) data. The hydration temperature of blended cement pastes was measured during the first 24 hours. Fresh and hardened concrete properties were tested. Compressive strength was determined and differential thermal analysis (DTA) was conducted of specimens at the age of 3, 14, 28 and 56 days.

Keywords: high performance concrete, pozzolanic additives, silica fume, ternary systems

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Authors: C. S. Paglia, E. Ginercordero, A. Jornet

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Environmental pollution, along with the depletion of natural resources, is among the most serious global challenges in our times. The construction industry is one of the sectors where a relevant reduction of the environmental impact can be achieved. Thus, the cement production will play a key role in sustainability, by reducing the CO₂ emissions and energy consumption and by increasing the durability of the structures. A large number of investigations have been carried out on blended cements, but it exists a lack of information on the Portland cement limestone - silica fume system. Mortar blends are optimized in the mix proportions for the different ingredients, in particular for the dosage of the silica fume. Portland cement and the new binder-based systems are compared with respect to the fresh mortar properties, the mechanical and the durability behaviour of the hardened specimens at 28 and 90 days. The use of this new binder combination exhibits an interesting hydration development with time and maintain the conventional characteristics of Portland cementitious material. On the other hand, it will be necessary to reproduce the Portland Limestone Cement-silica fume system within the concrete. A reduction of the CO₂ production, energy consumption, and a reasonable service life of the concrete structures, including a maintenance free period, will all contribute to a better environment.

Keywords: binder, cement, limestone, silica fume

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Authors: M. Saidi, I. Djefour, F. Ait Medjber, A. Melouane, A. Gacem

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The objective of this research is to study the physical and mechanical properties and durability of self-compacting mortars prepared by substituting a part of cement up to a percentage of 30% pozzolan according to different Blaine specific surface area (SSB1=7000 cm²/g and SSB=9000 cm²/g)). Order to evaluate durability, mortars were subjected to chemical attacks in various aggressive environments, a solution of a mixture of nitric acid and ammonium nitrate (HNO₃ + NH₄NO₃) and a magnesium sulfate salt solution (MgSO₄)) with a concentration of 10%, for a period of one month. This study is complemented by a comparative study of the durability of mortars elaborated with sulphate resistant cement (SRC). The results show that these mortars develop long-term, mechanical and chemical resistance better than mortars based Portland cement with 5% gypsum (CEM 1) and SRC. We found that the mass losses are lowest in mortars elaborated with pozzolanic cement (30% substitution with SSB₂) in both of chemical attack solutions (3.28% in the solution acid and 1.16% in the salt solution) and the compressive strength gains of 14.68% and 8.5% respectively in the two media. This is due to the action of pozzolan which fixes portlandite to form hydrated calcium silicate (CSH) from the hydration of tricalcic silicate (C₃S).

Keywords: aggressive environments, durability, mechanical strengths, pozzolanic cement, self-compacting mortar

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Authors: Mulubrhan Berihu

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Due to the design versatility, availability, and cost efficiency, concrete continues to be the most used construction material on earth. However, the production of Portland cement, the primary component of concrete mix is causing to have a serious effect on environmental and economic impacts. This shows there is a need to study using of supplementary cementitious materials (SCMs). The most commonly used supplementary cementitious materials are wastes, and the use of these industrial waste products has technical, economic, and environmental benefits besides the reduction of CO2 emission from cement production. This paper aims to document the effect on the strength property of concrete due to the use of low cement by maximizing supplementary cementitious materials like fly ash. The amount of cement content was below 250 kg/m3, and in all the mixes, the quantity of powder (cement + fly ash) is almost kept at about 500 kg. According to this, seven different cement content (250 kg/m3, 195 kg/m3, 150 kg/m3, 125 kg/m3, 100 kg/m3, 85 kg/m3, 70 kg/m3) with different amount of replacement of SCMs was conducted. The mix proportion was prepared by keeping the water content constant and varying the cement content, SCMs, and water-to-binder ratio. Based on the different mix proportions of fly ash, a range of mix designs was formulated. The test results showed that using up to 85 kg/m3 of cement is possible for plain concrete works like hollow block concrete to achieve 9.8 Mpa, and the experimental results indicate that strength is a function of w/b. The experiment result shows a big difference in gaining of compressive strength from 7 days to 28 days and this obviously shows the slow rate of hydration of fly ash concrete. As the w/b ratio increases, the strength decreases significantly. At the same time, higher permeability was seen in the specimens which were tested for three hours than one hour.

Keywords: efficiency factor, cement content, compressive strength, mix proportion, w/c ratio, water permeability, SCMs

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Authors: Martin Tazky, Rudolf Hela, Lucia Osuska, Petr Novosad

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Concrete’s volumetric changes are natural process caused by silicate minerals’ hydration. These changes can lead to cracking and subsequent destruction of cementitious material’s matrix. In most cases, cracks can be assessed as a negative effect of hydration, and in all cases, they lead to an acceleration of degradation processes. Preventing the formation of these cracks is, therefore, the main effort. Once of the possibility how to eliminate this natural concrete shrinkage process is by using different types of dispersed reinforcement. For this application of concrete shrinking, steel and polymer reinforcement are preferably used. Despite ordinarily used reinforcement in concrete to eliminate shrinkage it is possible to look at this specific problematic from the beginning by itself concrete mix composition. There are many secondary raw materials, which are helpful in reduction of hydration heat and also with shrinkage of concrete during curing. The new science shows the possibilities of shrinkage reduction also by the controlled formation of hydration products, which could act by itself morphology as a traditionally used dispersed reinforcement. This contribution deals with the possibility of controlled formation of mono- and tri-sulfate which are considered like degradation minerals. Mono- and tri- sulfate's controlled formation in a cementitious composite can be classified as a self-healing ability. Its crystal’s growth acts directly against the shrinking tension – this reduces the risk of cracks development. Controlled formation means that these crystals start to grow in the fresh state of the material (e.g. concrete) but stop right before it could cause any damage to the hardened material. Waste materials with the suitable chemical composition are very attractive precursors because of their added value in the form of landscape pollution’s reduction and, of course, low cost. In this experiment, the possibilities of using the fly ash from fluidized bed combustion as a mono- and tri-sulphate formation additive were investigated. The experiment itself was conducted on cement paste and concrete and specimens were subjected to a thorough analysis of physicomechanical properties as well as microstructure from the moment of mixing up to 180 days. In cement composites, were monitored the process of hydration and shrinkage. In a mixture with the used admixture of fluidized bed combustion fly ash, possible failures were specified by electronic microscopy and dynamic modulus of elasticity. The results of experiments show the possibility of shrinkage concrete reduction without using traditionally dispersed reinforcement.

Keywords: shrinkage, monosulphates, trisulphates, self-healing, fluidized fly ash

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Authors: Peter Thissen

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In this work, we report about the influence of the chemical potential of water on the carbonation reaction of wollastonite (CaSiO3) as model surface of cement and concrete. Total energy calculations based on density functional theory (DFT) combined with kinetic barrier predictions based on nudge elastic band (NEB) method show that the exposure of the water-free wollastonite surface to CO2 results in a barrier-less carbonation. CO2 reacts with the surface oxygen and forms carbonate (CO32-) complexes together with a major reconstruction of the surface. The reaction comes to a standstill after one carbonate monolayer has been formed. In case one water monolayer is covering the wollastonite surface, the carbonation is no more barrier-less, yet ending in a localized monolayer. Covered with multilayers of water, the thermodynamic ground state of the wollastonite completely changes due to a metal-proton exchange reaction (MPER, also called early stage hydration) and Ca2+ ions are partially removed from solid phase into the H2O/wollastonite interface. Mobile Ca2+ react again with CO2 and form carbonate complexes, ending in a delocalized layer. By means of high resolution time-of-flight secondary-ion mass-spectroscopy images (ToF-SIMS), we confirm that hydration can lead to a partially delocalization of Ca2+ ions on wollastonite surfaces. Finally, we evaluate the impact of our model surface results by means of Low Energy Ion Scattering (LEIS) spectroscopy combined with careful discussion about the competing reactions of carbonation vs. hydration.

Keywords: Calcium-silicate, carbonation, hydration, metal-proton exchange reaction

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Authors: Aurore Lechevallier, Mohend Chaouche, Jerome Soudier, Guillaume Renaudin

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The cement industry accounts for 8% of the global CO₂ emissions, and approximately 60% of these emissions are associated with the Portland cement clinker production from the decarbonization of limestone (CaCO3). Their impact on the greenhouse effect results in growing social awareness. Therefore, CO2 footprint becomes a product selection choice, and substituting Portland cement with a lower CO2-footprint alternative binder is sought. In this context, new hydraulic binders have been studied as a potential Ordinary Portland Cement substitute. Many of them are composed of iron oxides and aluminum oxides, present in the Ca₄Al₂-xFe₂+ₓO₁₀-like phase and forming Ca-LDH (i.e. AFM) as a hydration product. It has become essential to study the possible existence of Fe/Al AFM solid solutions to characterize the hydration process properly. Ca₂Al₂-xFex(OH)₆.X.nH₂O layered AFM samples intercalated with either nitrate or chloride X anions were synthesized based on the co-precipitation method under a nitrogen atmosphere to avoid the carbonation effect.AFM samples intercalated with carbonate anions were synthesized based on the anionic exchange process, using AFM-NO₃ as the source material. These three AFM samples were synthesized with varying Fe/Al molar ratios. The experimental conditions were optimized to make possible the formation of Al-AFM and Fe-AFM using the same parameters (namely pH value and salt concentration). Rietveld refinements were performed to demonstrate the existence of a solid solution between the two trivalent metallic end members. Spectroscopic analyses were used to confirm the intercalation of the targeted anion; secondary electron images were taken to analyze the AFM samples’ morphology, and energy dispersive X-ray spectroscopy (EDX) was carried out to determine the elemental composition of the AFM samples. Results of this study make it possible to quantify the Al/Fe ratio of the AFM phases precipitated in our hydraulic binder, thanks to the determined Vegard's law characteristic to the corresponding solid solutions

Keywords: AFm phase, iron-rich binder, low-carbon cement, solid solution

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Authors: Manju Verma, Parag A. Deshpande

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Electronic structure calculations of hydrogen terminated metal-porphyrin graphene were carried out to explore the catalytic activity for CO2 hydration reaction. A ruthenium atom was substituted in place of carbon atom of graphene and ruthenium chelated carbon atoms were replaced by four nitrogen atoms in metal-porphyrin graphene system. Ruthenium atom created the active site for CO2 hydration reaction. Ruthenium-porphyrin graphene followed the mechanism of carbonic anhydrase enzyme for CO2 conversion to HCO3- ion. CO2 hydration reaction over ruthenium-porphyrin graphene proceeded via the elementary steps: OH- formation from H2O dissociation, CO2 bending in presence of nucleophilic attack of OH- ion, HCO3- ion formation from proton migration, HCO3- ion desorption by H2O addition. Proton transfer to yield HCO3- ion was observed as a rate limiting step from free energy landscape.

Keywords: ruthenium-porphyrin graphene, CO2 hydration, carbonic anhydrase, heterogeneous catalyst, density functional theory

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