Influence of two different fly ashes on the hydration of portland cements

Fly ashes from the combustion of coal thermal power stations are commonly incorporated into portland cements and/or concretes and mortars. The chemical and morphological composition of fly ashes, together with their particle size, make them suitable as pozzolanic(non-calcic) or pozzolanic/hydraulic(highly calcic) additions to manufacture such building materials. This work focuses on the incorporation of two different fly ashes (non-calcic but of very different Fe₂O₃(%) contents, fineness and morphology) to two ordinary portland cements (of very different mineralogical composition as well), to determine the effects those have and the interactions they produce in the hydration reactions of portland cement. The main techniques employed for this study have been: conduction calorimetry and Frattini test; secondary techniques applied have also been: determination of setting times and analysis by X-ray diffraction and SEM. Analysis of the results obtained permitted to find different effects of fly ash addition on the hydration reactions of portland cements. Thus, dilution and stimulation effects augment with the increased fly ash percentage. Delay and acceleration of the reactions depend mainly on the type of portland cement and are accentuated with increased fly ash contents. Their behaviour as concerns heat dissipation mainly, depends on the type of fly ash used and is more pronounced with increased cement replacement. On the other hand, the pozzolanic activity of these fly ashes has been revealed at 7 and 28 days, but not at 2 days. Finally, pozzolanic cements can be manufactured using different portland cements and/or types of fly ashes, in the appropriate proportions and compatible qualities, depending on the effect(s) one wish to enhance at a specific age, which is according to previous general conclusions drew out of sulphate attack and chloride attack researches. This revised version was published online in July 2006 with corrections to the Cover Date.     

Study of hydration of two cements of different strengths

Main hydration products of two cement pastes, i.e. CSH-gel, portlandite (P) (and specific surface S) were studied by static heating, and by SEM, TEM and XRD, as a function of cement strength (C-33 and C-43) hydration time (th) and subsequent hydration in water vapour.Total change in mass on hydration and air drying, M_o, increased with strength of cement paste and with hydration time. Content of water escaping at 110 to 220°C, defined as water bound with low energy, mainly interlayer and hydrate water, was independent on cement strength but its content increased with (th). Content of chemically bound (zeolitic) water in CSH-gel, escaping at 220-400°C, was slightly dependent on strength and increased with (th). It was possibly derived from the dehydroxylation of CSH-gel and AFm phase. Portlandite water, escaping at 400-500°C, was independent on cement strength and was higher on longer hydration. Large P crystals were formed in the weaker cement paste C-33. Smaller crystals were formed in C-43 but they increased with (th). Carbonate formated on contact with air (calcite, vaterite and aragonite), decomposed in cement at 600-700^oC. It was high in pastes C-33(1 month) and C-43(1 month), i.e. 5.7 and 3.3%, respectively; it was less than 1% after 6 hydration months (low sensitivity to carbonation) in agreement with the XRD study showing carbonates in the air dry paste (1month), and its absence on prolonged hydration (6 months) and on acetone treatment. Water vapour treatment of (6 months) pastes or wetting-drying increased this sensitivity.Nanosized P-crystals, detected by TEM, could contribute to the cement strength; carbonate was observed on the rims of gel clusters.This revised version was published online in November 2005 with corrections to the Cover Date.     

Calorimetric studies of special cements

The kinetics and even the mechanism of cement reaction with water can be successfully investigated by use of microcalorimetry. In this study this method was applied to follow the hydration of the new family of portland cements containing C₁₂A₇ ^* and C₁₁A₇·CaF₂ addition as well as special cement with C₃A replacement by calcium sulphoaluminate. It has been found that C₁₁A₇·CaF₂ acted as hydration retarder. The heat evolution curves for C₁₂A₇ containing samples without CaF₂ are very similar to those for the reference portland cement samples. XRD and SEM studies confirm the results described above, relating to the retardation of alite hydration. The process is positively modified by the addition of anhydrite. In the presence of calcium sulphoaluminate (4CaO·3Al₂O₃·SO₃) the hydration at early stage occurs with the rapid formation of large amount of the ettringite phase. The calcium fluoride acts as a set retarder. The full compatibility of calorimetry with SEM and XRD results should be underlined. In cement chemistry the following notation is used:C=CaO,A=Al₂O₃,S=SiO₂,H=H₂O etc. for the main oxide constituents of portland cement clinker and hydrates.     

Calorimetric investigations on mound-building birds

Megapodes, and mound-building birds of the Pacific, incubate their eggs underground where the heat is supplied by organic decomposition, solar radiation, or geothermal sources. The incubation biology of the Australian mound builders has been examined from the standpoints of (1) the energetic requirements of malleefowl (Leipoa ocellata) to construct and maintain incubation mounds and (2) the physics, physiology, and behavior concerning mound thermoregulation of the brush turkey (Alectura lathami).

The energetic cost of mound tending in malleefowl is estimated by indirect calorimetry. The power required for digging into the mound to reach the eggs is approximately 20 W, or 3.8 times the basal metabolic rate of the bird. About 850 kg of sand has to be removed and replaced on the mound every time it is opened, a task requiring about 5 h. The overall energy investment for incubation for the entire 9 month season is 2.5 times that expected in similarly sized birds.

Brush turkey mounds become homeothermic because of (1) the high thermal inertia of their 3–11 t mass and (2) a stable equilibrium that is reached between heat production and heat loss. The mound tends to seek the equilibrium, but the bird adjusts the temperature by subtle manipulation of the mound. At an equilibrium temperature of 33°C, the mound produces about 110 W. Empirical data from natural mounds, set in the context of a numerical model of heat production and heat flux in the mound, indicate that equilibrium temperature is extremely sensitive to ambient temperature and mound size, but not water content. Wet or dry mounds can maintain appropriate incubation temperature, but the dry ones have low thermal conductivity, retain the heat well, and minimize the amount of forest litter collected during the incubation season.     

Studies on the influence of spent FCC catalyst on hydration of calcium aluminate cements at ambient temperature

The influence of spent catalyst from catalytic cracking in fluidized bed (FCC) on the hydration of two kinds of calcium aluminate cements (of about 40 and 70% content of alumina) was studied. Cement pastes were prepared with constant ratio of water/binder = 0.5 and with content of 0, 5 and 25% mass of addition as replacement of cement. The samples were stored at room temperature. Thermal analysis (TG, DTG), infrared absorption (FTIR) and X-ray diffraction methods were applied to investigate changes in various periods of hydration (up to 150 days). The compressive strength of cement mortars was also examined. On the basis of presented results it was affirmed that in studied conditions spent FCC catalyst is a reactive addition in calcium aluminate cement (CAC) pastes, which probably can create a new phase type C–A–S–H. It may be an interesting alternative for limitation of the negative phenomenon of conversion of aluminate hydrates, although the degree of the influence of the mineral additive depends on the composition of CAC and of the quantity of the used waste.     

Investigations of the influence of different fly ashes on cement hydration

Investigations of physico-chemical properties of three kinds of fly ash and their influence on cement hydration were performed in this work. Thermal analysis, microcalorimetry, infrared absorption and others were used. It was confirmed that the kind of coal and combustion conditions essentially influence physico-chemical properties of fly ash and in consequence influence cement hydration. Investigated fly ashes show in cement system so-called pozzolanic activity. Fly ash from combustion of brown coal in fluidized furnace revealed better activity compared to other investigated ones. This work is an introduction to more extensive investigation of fly ash activation.     

Calorimetric study of the native and postdenatured structures in starches with different degree of hydration

DSC studies of melting process of annealed native structures and postdenatured ones in low-amylose starches with different degrees of hydration were carried out. The starch recrystallization at different thermal treatments of the samples was studied both after the complete and partial destroy of native structures. It has been shown that native structures as well as postdenatured ones possess the ability to perfection, which is most clearly seen at the annealing at temperatures inside their melting ranges. The results obtained demonstrate that at the same duration of annealing the process of crystal perfection for secondary starch structures proceed more intensively compared to the native ones. The presence of the remained native structures in partial melt in contrast to the remained gel ones restricts the ability of the recrystallized structures to perfection.     

Calorimetric determination of the effect of additives on cement hydration process

Possibilities of a multicell isoperibolic-semiadiabatic calorimeter application for the measurement of hydration heat and maximum temperature reached in mixtures of various compositions during their setting and early stages of hardening are presented. Measurements were aimed to determine the impact of selected components?? content on the course of ordinary Portland cement (OPC) hydration. The following components were selected for the determination of the hydration behaviour in mixtures: very finely ground granulated blast furnace slag (GBFS), silica fume (microsilica, SF), finely ground quartz sand (FGQ), and calcined bauxite (CB). A commercial polycarboxylate type superplasticizer was also added to the selected mixtures. All maximum temperatures measured for selected mineral components were lower than that reached for cement. The maximum temperature increased with the decreasing amount of components in the mixture for all components except for silica fume. For all components, except for CB, the values of total released heat were higher than those for pure Portland cement samples.     

Heat of hydration prediction for blended cements

Prediction and control of concrete temperature rise due to cement hydration is of great significance for mass concrete structures since large temperature gradients between the surface and the core of the structure can lead to cracking thus reducing durability of the structure. Cement replacement with supplementary cementitious materials (SCMs) is frequently used to reduce the concrete temperature rise. Several models have been proposed for predicting heat release of blended cements; however, none of them address incorporation of metakaolin into the mixture. Isothermal calorimetry measurements, based on statistical experimental design, were taken on pastes incorporating combinations of SCMs and chemical admixtures. The data were then used to develop equations to predict the total heat reduction with the incorporation of chemical admixtures and SCMs. Analysis of the calorimetry data indicated that chemical admixtures do not have a significant effect on heat evolution beyond 12 h. SCMs investigated in this study (fly ash, slag, silica fume and metakaolin), on the other hand, were found to have a significant effect at hydration ages of 12, 24, 48 and 72 h.     

Synthesis of colloidal aluminosilicate for light-scattering investigations

To develop a binary colloidal system with a slight index of refraction mismatch suitable for light scattering studies, pure silica particles synthesized by the method of St?ber were mixed with aluminosilicate colloids synthesized using a novel approach. With this, index-matching for one component allowed extraction of the spatial distribution of the other. In addition, it was observed that by varying the solvent, interactions between colloids could be tuned from purely repulsive to weakly attractive.     

The influence of different additives on the early-stage hydration of calcium aluminate cement

The thermal decomposition behaviors of 2,4,6-Trinitrotoluene (TNT) and 1-methoxy-2,4-dinitro-benzene (DNAN) were studied by using a NETSCH company accelerating rate calorimetry. Hazard indicators such as onset temperature, adiabatic temperature rise, initial self-heat temperature, maximum self-heating rate, and time-to-maximum temperature rise rate have been determined directly. The kinetic parameters, such as the activation energy (E _a) and the pre-exponential factor (A) were studied from the measured self-heating rate data by assuming order reaction.     

Calorimetric measurements of adsorption power for active centers of aluminosilicate catalysts

Direct calorimetric measurements for the interaction energy of cumene and benzene with active centers of an aluminosilicate catalyst have been carried out to determine the potential energies of the centers catalyzing selective cracking with minimum coke formation. Kinetics of cumene cracking has been examined.

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Calorimetric comparison of portland cements containing silica fume and metakaolin

This new study must be regarded to be a direct outcome of two previous studies published by these same authors, which were conducted to respond to interesting questions brought out about the effect of silica fume, SF and metakaolins, M and MQ, on the heat of hydration of portland cements, PC, with very different C₃A and C₃S contents. The answer to these so interesting questions has been the primary objective of the present research. For this purpose, the same PC, PC1 (14% C₃A) and PC2 (≈0% C₃A), metakaolins, silica fume and blended cements were once again used more 60/40 for sulphate attack, and the same analytical techniques (CC, pozzolanicity and XRD analysis) and parameters determined as well. In this new research, the sulphate attack was determined by two accelerated methods: Le Chatelier-Ansttet and ASTM C 452-68. The experimental results of sulphate attack mainly, have demonstrated definitively that the high, rapid and early pozzolanic activity exhibited by SF also is, as in the case of the two metakaolins, more specific than generic, for it indirectly stimulated greater C₃A than C₃S hydration, but only in the first 16 h monitored in this study. Thereafter it is the contrary, i.e., anti- or contra-specific for the same purpose. And the longer the hydration time, the more anti- or contra-specific it became, since, when exposed to sulphate attack, SF blended cements resisted or even prevented the aggressive attack against PC1 which, with a higher C₃A content than PC2, was the more vulnerable of the two. By contrast, metakaolin MQ not only failed to hinder or prevent the attack, but heightened its effects, rendering it more intense, aggressive and rapid, leading to what could be called a rapid gypsum attack.     

Calorimetric investigations of hydrogen-bonded liquid crystal binary mixtures

Journal of Thermal Analysis and Calorimetry - Double hydrogen-bonded liquid crystals formed between methyl malonic acid (MM) and p-n-alkyloxy benzoic acids (nBAO) are characterized. Variation in...     

Synthesis and calorimetric study of hydration behavior of sulfate-rich belite sulfoaluminate cements with different phase compositions

Sulfate-rich belite sulfoaluminate (BSA) cements with varied phase compositions were synthesized in this work. The presence of sulfate in the clinker is in the form of anhydrite in addition to calcium sulfoaluminate. The aim of this paper is to study the effect of mineral composition on cement properties. Experimental results indicate that the improvement of early-age strengths mainly depends on the hydration of ye’elimite. The increase of ferrite content promotes the compressive strength after 7 days of hardening, but has adverse effect on cement strength at early ages. The optimum content of ferrite is between 10 and 20% for BSA cement containing approximately 35% ye’elimite. Different amounts of natural gypsum were added to the synthetic sulfate-rich BSA clinkers and we found that anhydrite formed in BSA clinkers can replace natural gypsum to facilitate the hydration of ye’elimite.