Influence of amorphous Al(OH)3 on the hydration of tricalcium aluminate

The influence of amorphous Al(OH)₃ on the hydration of tricalcium aluminate was investigated in pastes and in suspensions. In suspensions it was found that amorphous Al(OH)₃ started to dissolve almost immediately, and a stage was passed in which most of the anions present in the aqueous phase were polymeric aluminate units. Paste hydration results could be understood by assuming that highly soluble amorphous Al(OH)₃ dissolved and, by so doing, adjusted the concentrations in the aqueous phase so as to cause precipitation of some less soluble form of Al(OH)₃, thereby retarding hydration.     

Action of triethanolamine on the hydration of tricalcium aluminate

Hydration characteristics of tricalcium aluminate and tricalcium aluminate + gypsum were studied following addition of 0.5, 1.0, 5.0 or 10.0% triethanolamine (TEA) at a solution/C₃A ratio of 1.0 after hydration periods of 1 to 60 min. TEA accelerated the hydration of C₃A to the hexagonal aluminate hydrate and its conversion to the cubic aluminate hydrate. The rate of hydration increased with increased amounts of TEA, which also accelerated the formation of ettringite in the C₃A-gypsum-H₂O system.     

The effect of pozzolanas on the tricalcium aluminate hydration

The effect of pozzolanas on the C₃A hydration with and without lime and gypsum was examined. The addition of pozzolana lowers the heat evolution caused by C₃A hydration. Lime combination with C₃A and its hydration product is favoured by the addition of pozzolana, with a different mechanism of reaction depending on the presence of gypsum. Volcanic pozzolana in the presence of lime accelerates the transformation from hexagonal hydroaluminate to cubic C₃AH₆.     

Influence of sodium aromatic sulfonates on the hydration of tricalcium aluminate with or without gypsym

The influence of sodium aromatic sulfonates on the hydration of C₃A alone or plus gypsum was investigated specially relating to the molecular structure of the additives. It was found that the existence of sodium aromatic sulfonates retards the hydration of C₃A either with or without gypsum, and the degree of retardation depends upon the structures of sodium aromatic sulfonates.     

The effect of lignosulphonate fractions on the hydration of tricalcium aluminate

Two commercial calcium lignosulphonates have been separated into various fractions by ion exchange and dialysis. The effect of these fractions on the hydration of C₃A has been studied and the nature of the active fraction elucidated. It is concluded that aldonic acids are responsible for the greater part of the retardation of C₃A.     

Kinetics of hydration of tricalcium aluminate in the presence of gypsum

Based on a conceptual model for the stages of hydration of tricalcium aluminate in the presence of gypsum, a mathematical model was developed for the kinetics of hydration. The model was solved, illustrated and compared to experimental heat release data. Analytical equations were presented for the first two stages, while the last stages of hydration reduced to a previously developed model for the hydration of tricalcium aluminate in the absence of gypsum. Results suggested that pore diffusion through a thickening ettringite barrier layer controlled the first stage of hydration, while pore diffusion through a thinning ettringite barrier layer controlled the second stage. After the ettringite layer disappeared, the reaction of the remaining tricalcium aluminate proceeded more rapidly, but by a similar mechanism, than in the absence of sulfate containing species.     

Crystal structure refinement and hydration behaviour of doped tricalcium aluminate

In this paper analytical evidence on crystal structure and hydration behaviour of C₃A solid solutions with MgO, SiO₂, Fe₂O₃, Na₂O and K₂O is given. Samples were prepared using an innovative sol-gel process as precursor, examined by X-ray powder diffraction, infra-red spectroscopy and the crystal structure was refined by the Rietveld method. A significant shift of lattice parameters was found for C₃A solid solutions with SiO₂, Fe₂O₃ or Na₂O but only minor changes were detected for K₂O. The hydration of C₃A solid solutions in the absence of CaSO₄ was accelerated for samples doped with SiO₂ or K₂O and it was retarded in the case of MgO, Fe₂O₃ or Na₂O. The hydration in the presence of CaSO₄ was accelerated when C₃A was doped with K₂O or Na₂O, whereas Fe₂O₃ strongly retarded the hydration. The doping with SiO₂ nearly had no influence on the hydration, the effect of MgO was not straight forward.     

Structural and hydration properties of amorphous tricalcium silicate

Mechanical milling was carried out to synthesize amorphous tricalcium silicate (Ca₃SiO₅) sample, where Ca₃SiO₅ is the most principal component of Portland cement. The partial phase transformation from the crystalline to the amorphous state was observed by X-ray and neutron diffractions. Moreover, it was found that the structural distortion on the Ca-O correlation exists in the milled Ca₃SiO₅. The hydration of the milled Ca₃SiO₅ with D₂O proceeds as follows: the formation of hydration products such as Ca(OD)₂ rapidly occurs in the early hydration stage, and then proceeds slowly after about 15 h. The induction time for the hydration of the milled Ca₃SiO₅ is approximately one half shorter than that for the hydration of the unmilled one. This result means that the mechanical milling brings about the chemical activity of Ca₃SiO₅ for hydration, and may be particularly useful for increasing the reactivity in the early hydration stage.     

The effect of glucose and some glucose oxidation products on the hydration of tricalcium aluminate

The effect of glucose and some glucose oxidation products on tricalcium aluminate hydration has been studied. The results are in agreement with the theory that stabilization of hexagonal C₄AH₁₃ determines the retardation. It is assumed that the glucose oxidation products are more effective retarders than glucose because they are more stable in alkaline conditions.     

The tricalcium silicate hydration in the presence of active silica

The influence of active silica upon the tricalcium silicate hydration was studied. On the microcalorimetric curves a considerable acceleration of the process with dormant period elimination was observed. The reason for this is the lowering of calcium ions concentration in the solution as they are consumed, rapidly by the CSH phase formation of a low C/S ratio. Basing on these results the authors presume that the delaying factor of C₃S hydration process is the quasi-stationary layer supersaturated with calcium ions surrounding the anhydrous grains of tricalcium silicate.     

Influence of triethanolamine on the hydration characteristics of tricalcium silicate

The hydration characteristics of 3CaO.SiO₂ or β2CaO.SiO₂ are studied by an addition of 0.0, 0.1, 0.5 or 1.0% triethanolamine. The amount of Ca(OH)₂ found at 1, 3, 7 or 28 days was in the order C₃S + 0% TEA > C₃S +0.1% TEA > C₃S + 0.5% TEA > C₃S+1.0% TEA, irrespective of whether lime was estimated by X-ray, DTA, TGA or chemical analysis. The rate of hydration, in terms of the disappearance of 3CaO.SiO₂, showed that hydration proceeded faster in the presence of TEA after 1 day. Additions of TEA increase the induction period, promote the formation of a C-S-H with higher CaO/SiO₂ ratio, increase the formation of non-crystalline Ca(OH)₂ and enhance the surface area of the hydrated silicate product.     

Influence of pozzolanic additives on hydration mechanisms of tricalcium silicate

Pozzolanic mineral additives, such as silica fume (SF) and metakaolin (MK), are used to partially replace cement in concrete. This study employs extensive experimentation and simulations to elucidate and contrast the influence of SF and MK on the early age hydration rates of tricalcium silicate (triclinic C₃S), the major phase in cement. Results show that at low replacement levels (i.e., ≤10%), both SF and MK accelerate C₃S hydration rates via the filler effect, that is, enhanced heterogeneous nucleation of the main hydration product (C–S–H: calcium‐silicate‐hydrate) on the extra surfaces provided by the additive. The filler effect of SF is inferior to that of MK because of agglomeration of the fine particles of SF, which causes significant reduction (i.e., up to 97%) in its surface area. At higher replacement levels (i.e., ≥20%), while SF continues to serve as a filler, the propensity of MK to allow nucleation of C–S–H on its surface is substantially suppressed. This reversal in the filler effect of MK is attributed to the abundance of aluminate [Al(OH)₄^?] ions in the solution—released from the dissolution of MK—which inhibit topographical sites for C–S–H nucleation and impede its subsequent growth. Results also show that in the first 24 hours of hydration, MK is a superior pozzolan compared to SF. However, the pozzolanic activities of both SF and MK are limited and, thus, do not produce significant alterations in the early age hydration kinetics of C₃S. Overall, the outcomes of this study provide novel insights into the mechanistic origins of the filler and pozzolanic effects of SF and MK, and their impact on cementitious reaction rates.     

Influence of aluminium hydroxide and lime on the hydration of tricalcium silicate

Experiments by isothermal calorimetry, indicate that the hydration of 3CaO·SiO₂ (C₃S) is influenced very little by gibbsite; it is influenced by bayerite to a somewhat larger extent. In the presence of amorphous Al(OH)₃ the reaction of C₃S with water shows a very complicated course and gives four heat peaks. If CaO is added in addition to this Al(OH)₃, the third and the fourth heat peaks are more pronounced. From qualitative d.t.a., infra-red, electron-microscope and X-ray investigations, as well as from quantitative X-ray analysis, a reaction mechanism is proposed. The quantity of C₃S reacted, determined by means of quantitative X-ray analysis, is greater during the reaction of 2·00 g C₃S with 0·40 g amorphous Al(OH)₃, 0·08 g CaO and 2·00 ml water, than during the reaction of 2·00 g C₃S with 2·00 ml water.     

Cationic substitution in tricalcium aluminate

Cubic and orthorhombic crystals of tricalcium aluminate doped with Na₂O, Fe₂O₃ and SiO₂ were prepared and examined using an electron probe microanalyzer. The cationic ratios based on six oxygen atoms were derived from the oxide compositions. These data, together with those in previous studies for clinker aluminates containing Mg²⁺ and K⁺, provided excellent correlations between Al+Fe and Si (Al+Fe=2.001−1.03Si) and Ca+Mg and Na+K+Si [Ca+Mg=3.006−0.51(Na+K+Si)]. The chemical variation that is constrained by these equations is well accounted for by the general formula (Na,K)_2x(Ca,Mg)_3−x−y[(Al,Fe)_1−ySi_y]₂O₆, where x is the amount of Ca substituted by Na and K (0≤x<0.158), and y is the amount of Al substituted by Si (0≤y<0.136). The crystal system changed from cubic to orthorhombic with increasing x value. The substitution of Si and Fe for Al extended the solid solution range of the orthorhombic phase to lower values of x, while its effect on the solid solution range of the cubic phase was reversed.     

Influence of precuring on high pressure steam hydration of tricalcium silicate

Samples of C₃s, hydrated at room temperature for 0, 2, 4, 8 and 24 hours, were steam cured at 130, 160 and 190°C for 5, 15 and 24 hours, in order to assess the influence of preliminary curing on autoclave hydration. The room temperature curing duration affects the autoclave hydration of C₃S, mainly at low temperatures. The types and relative amounts of the obtained products are also markedly affected by the preliminary treatment.     

Studies on the hydration of tricalcium silicate pastes III. Influence of admixtures on hydration and strength development

A study has been made of the influence of calcium salts, as set-controlling admixtures, on the hydration of tricalcium silicate. It is found that some admixtures modify the morphology of C-S-H gel and for calcium hydroxide. Changes in capillary porosity distribution can be correlated with changes in the morphology of the outermost C-S-H gel. It is concluded that capillary porosity, as controlled by the degree of hydration is still the dominant factor controlling tensile strength.     

Influence of precuring on high pressure steam hydration of tricalcium silicate II. Effect of fineness of tricalcium silicate

C₃S samples of different fineness were precured at room temperature and subsequently autoclaved. It was found that, as the fineness is increased: 1) the effect of precuring on the hydration rate of C₃S in autoclave is less evident; 2) the precuring time corresponding to the highest amount of C₃SH_1.5 becomes longer; 3) particularly for short precuring times, the quantity of C₃SH_1.5 decreases and the formation of α-C₂SH is favored; 4) the amounts of the two crystalline hydrated silicates are reduced while the formation of CSH is favored.     

Combined effect of lignosulfonate and carbonate on pure portland clinker compounds hydration. III. Hydration of tricalcium silicate alone and in the presence of tricalcium aluminate

The effect of carbonate and/or lignosulfonate on the hydration of C₃S alone and in the presence of C₃A has been examined by DTG and TG curves and by zeta potential measurements. The combined addition of sodium carbonate and lignosulfonate strongly retards C₃A hydration. However by mixing 20 % C₃A with C₃S the retarding effect is significantly lower. On the other hand the early C₃A hydration is completely blocked by sodium carbonate and lignosulfonate simultaneously added. It seems that the fluidifying effect of the combined addition of those admixtures could be ascribed to both the dispersing action and the completely blocking effect on the early C₃A hydration.     

Evidence of calcium silicoaluminates in hydrated mixtures of tricalcium silicate and tricalcium aluminate

Calcium monosilicoaluminate C₃A·CaSiO₃·12 H₂O and calcium trisilicoaluminate C₃A·3 CaSiO₃·31 H₂O have been identified in pastes of C₃S + C₃A. Electron probe microanalysis and scanning electron microscopy with energy X-ray dispersive analysis show that silicoaluminates are both formed around C₃A grains by diffusion of silicate ions from C₃S grains through solution. In samples containing gypsum, these silicate ions diffuse through the sulfoaluminate zone.     

Modification on the tricalcium aluminate phase in cements by manganese substitution

The effect of manganese substitution into the crystal structure of the tricalcium aluminate Ca₃Al₂O₆ has been studied by X-ray, analytical electron microscopy, IR spectroscopy and electronic spin resonance. The limit of solid solution of manganese in this phase was determined. The formula proposed for this solubility is (Ca_2.984Mn_0.016)(Al_1.979Mn_0.021)O₆. In presence of CaO and Al₂O₃ the manganese reacts to give Ca₂AlMnO₅ phase, reducing appreciably tricalcium aluminate contents.