Studies of Early Stages of Paste Hydration of Cement Compounds, II

The paste hydration of mixtures of alite, C₃A, and C₄AF with and without gypsum and/or NaOH was studied by electron-optical and X-ray diffraction techniques. In the absence of both gypsum and NaOH, a foil-like reaction product and hexagonal calcium aluminate hydrates were formed first. Any CO₂, present formed calcium carboaluminate. With time the foils changed to splines of CSH, and hexagonal aluminate hydrates changed to cubic C₃AH₆. When no gypsum was present, NaOH solution retarded the formation of hexagonal aluminates at the very early stages of hydration; it did not have much effect on the later hydration processes. With gypsum but without alkali, a foil-like product and ettringite formed first. Later the foils changed to splines of CSH and ettringite to monosulfate. Alkali, in the presence of gypsum, hastened the formation of splines of CSH. The results suggest that the hydration of alite, even after 14 days, goes through the solution phase.     

Kinetics of Tricalcium Aluminate and Tetracalcium Aluminoferrite Hydration in the Presence of Calcium Sulfate

Hydration reactions of C₃A and C₄AF with calcium sulfate hemihydrate and gypsum were investigated and the kinetics of the reactions compared. The rates of C₃A and C₄AF hydration, as determined by heat evolution, vary depending on whether the sulfate-containing reactant is gypsum or calcium sulfate hemihydrate. The following sequence of reactions involving C₄AF occurs when hemihydrate is the reactant: gypsum formation during the first hour, ettringite formation between 20 and 36 hours, and the conversion of ettringite to monosulfate over a period of about 12 hours. Monosulfate formation initiates prior to the complete consumption of gypsum. The onset of this conversion occurs at a shorter hydration time when hemihydrate is a reactant and the total amount of heat evolved is lower. The hydration reactions in saturated calcium hydroxide solution occur more slowly than those in water. Based on heat liberation, C₄AF reacts at a much higher rate than C₃A. Ettringite formation occurs during the first 8 to 9 days of C₃A hydration. Once the gypsum is consumed, ettringite converts to monosulfate during two additional days. Compared to gypsum, hemihydrate decreases the rates of hydration of both C₃A and C₄AF. The effects on the hydration characteristics of C₄AF are significant. The hydration of C₃A with gypsum in water, in saturated Ca(OH)₂ solution, and in 0.3 M NaOH solution were compared. Heat evolution is the lowest for hydration in 0.3 M NaOH. The onset of monosulfate formation occurs prior to the complete reaction between gypsum and C₃A in the NaOH solution.     

Early Hydration of Tetracalcium Aluminoferrite in Gypsum and Lime-Gypsum Solutions

Based on product compositions and on the compositional changes occurring in the aqueous phase, a mechanism for the early hydration of C₄AF in solutions containing gypsum or lime and gypsum is suggested. According to this mechanism, early formation of AFt is preceded by the formation of alumina gel or C₂AH₈. Early AFt formation occurs through solution, and the early AFt product contains little or no iron. The solution chemistry also suggests that an amorphous, iron-rich gel forms and that calcium is associated with this gel.     

Hydration of Beta Dicalcium Silicate Alone and in the Presence of CaCl2 or C2H5OH

Beta C₂S was hydrated at room temperature with and without added CaCl₂ or C₂H₅OH by methods previously studied for the hydration of C₃S, i.e. paste, bottle, and ball-mill hydration. The amount of reacted β-C₂S, the Ca(OH)₂ concentration in the liquid phase, the CaO/SiO₂ molar ratio, and the specific surface area of the hydrate were investigated. A topochemical reaction occurs between water and β-C₂S, resulting in the appearance of solid Ca(OH)₂ and a hydrated silicate with a CaO/SiO₂ molar ratio of ≃1. As the liquid phase becomes richer in Ca(OH)₂, the first hydrate transforms to one with a higher CaO/SiO₂ ratio. Addition of CaCl₂ increases the reaction rate and the surface area of the hydrate but to a much lesser extent than in the hydration of C₃S, whereas C₂H₆OH strongly depresses the hydration rate of β-C₂S, as observed for C₃S hydration.     

Adsorption of Admixtures on Portland Cement Hydration Products

The adsorption of calcium lignosulfonate and salicylic acid was studied on the hydration products of the four principal components of portland cement. To investigate the adsorption as a function of development of hydration product, the determinations were made after varying hydration times. The times allowed were from 5 min to 24 hr for tricalcium aluminate (C₃A) and tetracalcium aluminoferrite (C₄AF) and from 1 hr to 28 days for β-dicalcium silicate (β-C₂S) and tricalcium silicate (C₃S). Samples were characterized with respect to surface area and poresize distribution. The effect of gypsum on the adsorption was also investigated. The results indicate that the amounts of salicylic acid and calcium lignosulfonate adsorbed on the hydration products of C₃A, and of calcium     

Effect of Organic Compounds on the Interconversions of Calcium Aluminate Hydrates: Hydration of Tricalcium Aluminate

The paste hydration of tricalcium aluminate (C₃A) in the presence of organic compounds was investigated at several temperatures up to 75°C. The results confirm earlier hypotheses that the hexagonal calcium aluminate hydrates (principally C₄AH₁₃) which are first formed create a protective barrier around the remaining C₃A and severely restrict further hydration. Above 30°C, conversion to C₃AH₆ breaks down this barrier and causes rapid hydration of C₃A. Organic compounds retard the hydration of C₃A by inhibiting the conversion reaction. Experiments with synthetic C₄AH₁₃ showed that organic molecules can form interlayer compounds, and it is considered that random sorption into the C₃AH₁₃ structure restricts the transformation to C₃AH₆. Other aspects of C₃A hydration and of the reactivity of C₄AH₁₃ are also discussed.     

Thermal Study of the Effect of Additives on the Hydration of Tricalcium Silicate

The rate of paste hydration of 3C_aO·SiO₂ (C₃S) and the effects of additions of CaCl₂, CdI₂, and CrCl₃, were studied by differential thermal analysis and thermogravimetry. X-ray analyses were used to identify the synthesized C₃S. The salts CaCl₂, CdI₂, and CrCl₃, accelerated the hydration of C₃S. The degree of hydration was estimated by the amount of Ca(OH)₂, formed, as determined by TG.     

Influence of SO3 on the Phase Relationship in the System CaO–SiO2–Al2O3–Fe2O3

The influence of the additive SO₃ on the phase relationships in the quaternary system CaO-SiO₂-Al₂O₃-Fe₂O₃ was investigated by observing the change of volume ratio of 3CaOSiO₂ (C₃S) to 2CaOSiO₂ (C₂S) + CaO (C) in the sintered material with the increase of SO₃ content. The primary phase volume of C₃S in the quaternary phase diagram shrank with the increase of SO₃ and disappeared when the SO₃ content exceeded 2.6 wt% in the sintered material. Changes in the peritectic reaction relationship between CaO (C), 2CaOSiO₂ (C₂S), 3CaOSiO₂ (C₃S), 3CaOAl₂O₃ (C₃A), 4CaOAl₂O₃Fe₂O₃ (C₄AF), and liquid were also observed and discussed.     

Character of Hydration of 3CaO.Al2O3

The C₃A compacts were hydrated and the reaction was studied by DTA, X-ray diffraction, mercury porosimetry, and volume change analysis. The hexagonal hydroaluminates C₂AH₈ and C₄AH₁₉ formed at 2°, 12°, and 23°C by a direct mechanism between C₃A and H₂O. The hydration reaction at 52° and 80°C was stopped by formation of C₃AH₆ around the C₃A grains. The rate of conversion of the hexagonal hydrates to cubic C₃AH₆ increased with temperature. Volume change analysis confirmed that C₃AH₆ grows epitaxially on the surface of the C₃A grain. The reaction at this surface and the passage of water through the layer of hexagonal hydroaluminates control the overall reaction rate. The conversion of the hexagonal hydrates to C₃AH₆ accelerates the reaction by removing the layer of products from around the C₃A grain by a solution mechanism. At 52° and 80°C, C₃AH₆ may form without the intermediate formation of the hexagonal hydrate.     

Direct Synthesis and Hydration of Calcium Aluminosulfate (Ca4Al6O16S)

Calcium aluminosulfate (Ca₄Al₆O₁₆S or C₄A₃̄) was prepared by direct synthesis from calcium and aluminum nitrates, and aluminum sulfate. CaAl₄O₇(CA₂) formed as an intermediate at 900°C, and C₄A₃̄ was the main phase after calcination at 1100°C. The specific surface areas after calcination at 1100° and 1300°C were ∼2.5 and 1 m²/g, respectively. Hydration was investigated using XRD, DSC, SEM, conduction calorimetry, and solid-state ²⁷Al MAS-NMR spectroscopy. Calorimetry showed that the induction period was longer than that of a sample prepared using conventional solid-state sintering, and this was attributed to the formation of amorphous coatings. Crystalline hydration products, principally calcium monoaluminosulfate hydrate and aluminum hydroxide, appeared subsequently. Although the induction period was very long, complete hydration occurred as early as 3 d in the sample calcined at 1100°C and was 91% complete in the sample calcined at 1300°C.     

Interaction Between Superplasticizers and Calcium Aluminate Hydrates

Sodium lignosulfonate and naphthalene and melamine sulfonate formaldehyde condensates, dissolved in lime water, are adsorbed on C₄AH₁₃ and C₃AH₆. When dissolved in dimethylsulfoxide the same admixtures are adsorbed on C₄AH₁₃ but, apparently, not on C₃AH₆. The adsorption isotherms of the two polycondensates are very similar but different from those of lignosulfonate. This fact can be attributed to the considerable structural difference between the synthetic admixtures and the lignine derivative. The particle zeta potential is modified by the presence of the admixtures, minimum additions of which are enough to bring the zeta potential to negative constant values. Nevertheless, the values of the potential cannot be correlated with the viscosity of the aluminate hydrate pastes, since the viscosity first increases and then decreases as the admixture increases. This behavior can be explained by a bridging effect among the particles, which overcomes the repulsive effect due to zeta potential.     

Synthesis and Hydration Characteristics of Alinite Cement

A chlorine-bearing alinite cement was synthesized using reagent-grade chemicals, and the phase evolution and hydration behavior of the alinite clinker were examined. The effects of the MgO content on alinite formation and hydration also were investigated. Alinite began to appear at 1000°C from β-C₂S, C₁₁A₇CaCl₂, and unreacted raw materials, and an almost single-phase alinite was obtained at 1300°C. The alinite phase also was produced without MgO addition. However, CaO, β-C₂S, and C₁₁A₇CaCl₂ phases were present. Alinite cements hydrated rapidly after a short incubation period, and the hydration products were C-S-H gels, Ca(OH)₂, and a Fridel's saltlike phase. The local environmental changes of silicon and aluminum during the formation and hydration of alinite were determined using magic-angle-spinning nuclear magnetic resonance spectroscopy. The Cl⁻-ion exsolution from the alinite paste during hydration was measured using ion chromatography.     

Kinetics of the Hydration of Tricalcium Silicate

The hydration of tricalcium silicate was followed at a water/C₃S ratio of 0.7 between 5° and 50°C by determining free lime and combined water. Free lime was estimated by the o -cresol method, whereas combined water was calculated from the amount of free water remaining in the paste as determined by extraction with methyl ethyl ketone. The ratio of free lime to combined water was constant throughout the hydration; this ratio indicated that CSH(II) may be represented as 1.68CaO · SiO₂· 2.58H₂O. When maximum supersaturation of the solution with Ca^2+] is attained, the induction period terminates and the reaction proceeds rapidly, probably as the result of propagative surface nucleation-growth of CSH(II). Kinetic equations were derived for these reactions. When the surface of C₃S is entirely covered by CSH(II), the reaction becomes slow and is controlled by diffusion of water. Constants involved in the kinetic equations are evaluated and discussed.     

Application of Selective 29Si Isotopic Enrichment to Studies of the Structure of Calcium Silicate Hydrate (C-S-H) Gels

Selective isotopic enrichment of SiO₂ with ²⁹Si in a mixture with tricalcium silicate (C₃S) has allowed the Si from this phase to be effectively labeled during the course of the hydration reaction, thus isolating its contribution to the reaction. A double Q₂ signal has been observed in ²⁹SI solid-state MAS NMR spectroscopy of C-S-H gels of relatively low Ca/Si ratio, prepared by hydration or by carbonation of a C₃S paste. The origin of the weaker, downfield peak is discussed and tentatively attributed to bridging tetrahedra of a dreierkette silicate chain structure.     

Preparation of Portland Cement Components by Poly(vinyl alcohol) Solution Polymerization

The four components portland cement-dicalcium silicate, C₂S (Ca₂SiO₄); tricalcium silicate, C₃S (Ca₃SiO₅); tricalcium aluminate, C₃A (Ca₃Al₂O₆); and tetracalcium aluminate iron oxide, C₄AF (Ca₄Al₂Fe₃O₁₀)-were formed using a solution-polymerization route based on poly(vinyl alcohol) (PVA) as the polymer carrier. The powders were characterized using X-ray diffraction techniques, BET specific surface area measurements, and scanning electron microscopy. This method produced relatively pure, synthetic cement components of submicrometer or nanometer crystallite dimensions, high specific surface areas, as well as extremely high reactivity at relatively low calcining temperatures. The PVA content and its degree of polymerization had a significant influence on the homogeneity of the final powders. Two types of degree of polymerization (DP) PVA were used. Lower crystallization temperatures and smaller particle size powders were obtained from the low-DP-type PVA at optimum content.     

Influence of Citric Acid on Reactions in the System 3CaO·Al2O3-CaSO4·2H2O-CaO-H2O

The influence of citric acid on paste hydration of 3CaO· Al₂O₃ in the presence of CaSO₄·2H₂O and Ca(OH)₂ was studied using X-ray diffraction, scanning electron microscopy, and conduction calorimetry. The time at which the citric acid is added (either prior to or with the mixing water) determines how it affects the reactivity of the aluminate. Immediately after the paste is gaged citric acid promotes a more rapid reaction, but later reactions are retarded. Hexagonal calcium aluminate hydrates, ettringite, and monosulfate were all detected as early hydration products. The influence of citric acid on the hydration of 3CaO·Al₂O₃ slabs immersed in saturated CaSO₄·2H₂O solutions was also studied and a reaction scheme proposed.     

Hydration of Tricalcium Silicate

The kinetics of paste, bottle, and ball-mill hydration of 3CaO SiO₂ and the effects of additions of electrolytes and alcohols were studied. Paste and bottle hydrations proceed through periods of induction, acceleration, and decay. If 3CaO SiO₂ is hydrated in an excess of H₂O, as in bottle hydration, the reaction rate is lower than that for paste hydration. The ball-mill hydration rate is much the highest and is controlled by the removal of the hydrate layer coating the 3CaO SiO₂ particles. Electrolytes always accelerate and alcohols retard the reaction rate. Experimental results are discussed with reference to modern theories of the 3CaO SiO₂ hydration mechanism.     

Early Formation of Ettringite in Tricalcium Aluminate–Calcium Hydroxide–Gypsum Dispersions

The formation of hydrates in dispersions of cubic tricalcium aluminate (C₃A)–calcium hydroxide–gypsum was observed using soft X-ray transmission microscopy. This technique allows the continuous imaging of the hydration process without the introduction of drying artifacts. Within minutes, microcrystalline hydrates covered the C₃A particles but over time large prismatic ettringite crystals are precipitated suppressing the microcrystalline hydrates. Within the resolution of the technique, no protective hydrated layer on the surface of C₃A particles was observed.     

Hydration in the System Ca2SiO4–Ca3(PO4)2 at 90°C

Compositions along the Ca₂SiO₄–Ca₃(PO₄)₂ join were hydrated at 90°C. Mixtures containing 15, 38, 50, 80, and 100 mol% Ca₃(PO₄)₂ were fired at 1500°C, forming nagelschmidtite + a ¹-CaSiO₄, A -phase and silicocarnotite and a -Ca₃(PO₄)₂, respectively. Hydration of these produces hydroxylapatite regardless of composition. Calcium silicate hydrate gel is produced when Ca₂SiO₄≠ 0 and portlandite when Ca₂SiO₄ is >50%. Relative hydration reactivities are a -Ca₃(PO₄)₂ > nagelschmidtite > α ¹-Ca₂SiO₄ > A -phase > silicocarnotite. Hydration in the presence of silica or lime influences the amount of portlandite produced. Hydration in NaOH solution produces 14-A tobermorite rather than calcium silicate hydrate gel.     

The Pore Structure of Hydrated Cementitious Compounds of Different Chemical Composition

The pore structure ofβ-C₂S, C₃S, and portland cement pastes was investigated using mercury porosimetry and H₂O and N₂ adsorption. The β-C₂S had more total macro- and mesoporosities than C₃S and portland cement pastes of a similar degree of hydration. C₃S and portland cement pastes had similar total porosities but differed in the porosity size distribution. In the mesopore range, the various test methods gave different results. These differences are discussed on the basis of the various models proposed for cement paste. It is shown that shrinkage could be correlated with the volume of pores <0.03 μm, but not with total porosity.