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.     

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.     

Phase Composition of Hydrated DSP Cement Pastes

Cement pastes densified with small particles (DSP) containing up to 48% silica fume by weight of cement, and hydrated to up to 180 d at room temperature, have been analyzed using TMS-GPC, TGA, and ²⁹Si NMR to quantitatively estimate the amount of unreacted cement, Ca(OH)₂, and residual silica fume, respectively. Using a mass balance approach, the CaO/SiO₂ and H₂O/SiO₂ molar ratios of the C-S-H in the samples were calculated. For samples containing silica fume, the values of CaO/SiO₂ lie between 0.9 and 1.3, depending on the degree of hydration and silica fume content, whereas for samples without silica fume they were 1.6. Silicate polymerization analysis using TMS-GPC suggests that the molecular structure of the C-S-H is similar to that formed in conventional hydration. No cross-linking species were found, but the fraction of higher polymers (above octamer) increases as the CaO/SiO₂ ratio decreases.     

Origin and Growth Kinetics of Platelike Abnormal Grains in Liquid-Phase-Sintered Alumina

The grain-growth behavior of Al₂O₃ compacts with small contents (≤10 wt%) of various liquid-forming dopants was studied. Equiaxed and/or elongated grains were observed for the following dopants: MgO, CaO, SiO₂, or CaO + TiO₂. The platelike grains, defined as the abnormal grains larger than 100 μm with an aspect ratio ≥5 and with flat boundaries along the long axis, were observed when the boundaries were wet with the liquid phase and the codoping satisfied two conditions of size and valence. These dopings were Na₂O + SiO₂, CaO + SiO₂, SrO + SiO₂, or BaO + SiO₂. However, an addition of MgO to the Al₂O₃ doped with CaO + SiO₂ resulted in the change of grain shape from platelike to equiaxial. Equiaxed grains were also observed for the MgO + SiO₂ doping, indicating that two conditions were necessary but not sufficient to develop the platelike grains. The fast growth rate of the platelike grains was explained by an increased interfacial reaction rate due to the codopants. AT the same time the codopants made the basal plane, which appeared as the flat boundaries, the lowest energy plane. The appearance of the platelike grains was favored in compacts with a small grain size and with a narrow size distribution at the onset of abnormal grain growth. Accordingly, the use of starting powders with a small particle size and narrow size distribution, smaller amounts of dopings, and high sintering temperature resulted in an increased number of the platelike grains.     

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.     

Crystallization of MgO-CaO-SiO2-P2O5 Glass

The crystallization behavior of a glass with a composition of 40 wt% 3CaO · P₂O₅−60 wt% CaO · MgO · 2SiO₂ was investigated. The primary crystalline phase was apatite with a dendritic form and ellipsoidal shape. β-(3CaO · P₂O₅) and CaO · MgO · 2SiO₂ were crystallized as samples heated to 990°C, and a three-layer structure was obtained. The development and morphology of this construction were explained by both the surface crystallization of the apatite and CaO · MgO · 2SiO₂ and the bulk crystallization of apatite and the CaO · MgO · 2SiO₂-β-(3CaO · P₂O₅) composite.     

Accelerated Curing of Compacted Calcium Silicate Mortars on Exposure to CO2

The parameters affecting strength development in compacted cylinders of 3CaO- SiO₂ and β-2CaO- SiO₂ mortars exposed to CO₂ were investigated. Strength increased with time up to 81 min, the duration of the longest detailed study. The β-2CaO- SiO₂ develops strength more slowly initially, but both silicates achieved compressive strengths of 7,000 to 10,000 psi. The rate of increase in strength depends on both the amount of water used in molding the compact and the amount of water present in the CO₂. Increasing CO₂ pressures from 1 to 2 atm increased the rate of reaction, but a further increase to 4 atm had little additional effect. Carbonation occurs mainly in the outer portions of the cylindrical compacts. The initial reaction on exposure to CO₂ appears to be accelerated hydration of the silicates to a CaO-SiO₂-H₂O-like gel and calcite. The gel has a stoichiometry similar to that found in conventional hydration. Further reaction results in progressive carbonation of the gel, which decreases its lime content. The reaction products appear to be intimately dispersed in the microstructure.     

Phase Equilibrium Diagram CaO—CaF2—2CaO.SiO2

Differential thermal analysis and quenching experiments were used to establish the ternary phase diagram CaO-CaF₂-2CaO.SiO₂. Hermetically-closed platinum capsules were used to prevent fluorine loss in the form of HF, SiF₄, and CaF₂ by reaction of the CaF₂ with water vapor or SiO₂, or by evaporation. The melting point of pure CaF₂ was 1419°± 1°C. There is one binary eutectic in the system CaO-CaF₂ and there are two ternary eutectics in the system CaO-CaF₂-2CaO.SiO₂. The results of the present study were combined with literature data to construct the phase diagram CaO-CaF₂-SiO₂.     

Analytical Electron Microscopic Studies of Doped Dicalcium Silicates

Dicalcium silicates having CaO/SiO₂ molar ratios of 1.8 to 2.2 were sintered at 1450°C for 90 min with or without small quantities of dopants (K₂O or Al₂O₃) and were air quenched. The microstructures of the fired samples were characterized using electron microscopy (SEM and TEM) and associated microanalytical techniques. There was no evidence for the existence of Ca_1.8SiO_3.8 or Ca_2.2SiO_4.2. Amorphous grain-boundary phases were observed between grains and as inclusions within the grains; the amounts decreased as CaO/SiO₂ ratios increased. The compositions of the amorphous phases were always rich in dopants and had a CaO/SiO₂ ratio close to that of wollastonite. High levels of Al₂O₃ were observed to enter the β-Ca₂SiO₄ grains under lime-rich conditions (CaO/SiO₂= 2.2) up to a saturation level of about 3.0 wt%. Some additional crystalline phases were observed to form depending on stoichiometry and dopant level.     

Effect of CaO on the Thermal Conductivity of Aluminum Nitride

The effect of CaO on the thermal conductivity of aluminum nitride pressureless sintered with 3 wt% Y₂O₃ as a sintering aid was investigated. Over the composition range of 0 to 2.0 wt% additions, CaO decreased the thermal conductivity of the sintered parts by 10%. CaO doping rendered the secondary oxide phases more wetting and thus with a greater tendency to penetrate along the grain boundaries. Furthermore, CaO segregation to the grain boundaries was observed even on those grain boundaries apparently free of secondary phases. These microstructural changes disrupted the connectivity of the high thermal conductivity AIN grains and were the main factors contributing to the decrease in the thermal conductivity of the ceramic parts. CaO additions to samples doped with SiO₂ had the opposite effect, increasing the thermal conductivity. CaO removed SiO₂ from the AIN grains and incorporated it into the oxide second phases, most likely through charge-compensating substitutions Ca²⁺+ Si⁴⁺ for Y³⁺ and/or Al³⁺. Thus, AIN samples containing both SiO₂ and CaO had higher thermal conductivity than those containing comparable amounts of SiO₂ alone.     

Crystal Chemistry of Hydrous Calcium Silicates: I, Substitution of Aluminum in Lattice of Tobermorite

Mixtures of 0.8 moles of CaO per mole of SiO₂ plus Al₂O₃ were prepared from lime, kaolin, and tripoli (microcrystalline quartz); the amounts of SiO₂ to Al₂O₃ were varied to give from 0.2 to 20.7% Al₂O₃ by weight of dry solids. After hydrothermal treatment (170° to 175°C.), the products were examined by differential thermal analysis and by X-ray diffraction. A homogeneous solid identified as the mineral tobermorite (4CaO.5SiO₂.5H₂O) and containing up to 4 or 5% Al₂O₃ was obtained. Increasing the amount of Al₂O₃ in the raw mixture above about 5% resulted in the formation of the hydrogarnet 3CaO.Al₂O₃.SiO₂.4H₂O as a second phase. Allowing for the Al₂O₃ combined in this solid, it was indicated that slightly more Al₂O₃ was substituted in the tobermorite as the amount was increased in the raw mixture. It is suggested that the Al³⁺ ions probably assume tetrahedral coordination when substituting for the Si⁴⁺ ions.     

Reaction of Beta-Dicalcium Silicate and Tricalcium Silicate with Carbon Dioxide and Water Vapor

The carbonation-reaction kinetics of beta-dicalcium silicate (2CaO·SiO₂ or β-C₂S) and tricalcium silicate (3CaO. SiO₂ or C₃S) powders were determined as a function of material parameters and reaction conditions and an equation was developed which predicted the degree of reaction. The effect of relative humidity, partial pressure of CO₂, surface area, reaction temperature, and reaction time on the degree of reaction was determined. Carbonation followed a decreasing-volume, diffusion-controlled kinetic model. The activation energies for carbonation of β-C₂S and C₃S were 16.9 and 9.8 kcal/mol, respectively. Aragonite was the principal carbonate formed during the reaction and the rate of carbonate formation was coincident with depletion of the calcium silicates; C-S-H gel formation was minimal.     

Quaternary System Al2O3–CaO–MgO–SiO2: I, Study of the Crystallization Volume of Al2O3

Compatibility relations of Al₂O₃ in the quaternary system Al₂O₃–CaO–MgO–SiO₂ were studied by firing and quenching followed by microstructural and energy-dispersive X-ray examination. A projection of the liquidus surface of the primary phase volume of Al₂O₃ was constructed in terms of the CaO, SiO₂, and MgO contents of the mixtures recalculated to 100 wt%. Two invariant points, where four solids coexist with a liquid phase, were defined, and the positions of the isotherms were tentatively established. The effect of SiO₂, MgO, and CaO impurities on Al₂O₃ growth also was studied.     

Thermodynamics of Calcium Silicate Hydrates and Their Solutions

The solution that surrounds hydrating cement particles contains dissolved species which are important in the overall process. A method, based on the Gibbs-Duhem equation for a three-component system, has been developed for computing the composition of one phase from values for its equilibrium solubility in a second phase. The method has been used to compute the CaO:SiO₂ ratio for two types of calcium silicate hydrate (C-S-H) gel, one of which is thought to form from hydrating tricalcium silicate (Ca₃SiO₅), and the other by precipitation from appropriate solutions. The results agree well with measured values reported in the literature. They have also been used to help define the probable composition of the C-S-H layer which forms on tricalcium silicate surfaces during the early stages of hydration when the reaction is slow. A chemical potential phase diagram is constructed from which thermodynamic quantities can be computed directly. The free energies of formation have been estimated for two types of C-S-H formed from CaO, SiO₂, and H₂O, These results provide insight into the structure and composition of C-S-H, which is the most abundant product in portland cement systems.     

Stability of the Aluminum Silicates

From the ternary phase diagrams of Al₂O₃–SiO₂ with CaO, MgO, or FeO, it can be concluded that the free energies of formation of kyanite, andalusite, and sillimanite, according to the reaction Al₂O₃+ SiO₂= Al₂O₃.SiO₂, are of the order of magnitude of 0 to –10 kcal. rather than the previously accepted value of –40 to –45 kcal. However, this result may be expected from the general variation of free energies of formation with the ionic potential of the silicate-forming cation; this conclusion is supported by a plot for some silicates, carbonates, and sulfates.     

Wollastonite from Hydrothermally Synthesized Calcium Hydrometasilicate Obtained from Various Modifications of Silica

A hydrothermally CaO–SiO₂–H₂O system was investigated at 150°–200°C, 2.5 h (CaO:SiO₂=0.95) using various modifications of SiO₂ in the presence of a mineralizer. Synthetic (stabilized) γ-tridymite is the most reactive among SiO₂ modifications. In the reaction mixture, the optimal concentration of the mineralizer (KOH) is 2% (versus the solid phase). The binding degree of CaO with SiO₂ practically is 100% at 150°C. It is impossible to synthesize CSH free of C₂SH on the basis of β-cristobalite and β-quartz under the investigation conditions without the use of mineralizer. The calorimetric effects as well as heat of de-hydration of hydrosilicates were determined during their transformation into wollastonite. The entropy change at the peaks has been calculated.     

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.     

Effect of Additives on the Pressureless Sintering of Aluminum Nitride between 1500° and 1800°C

Combined oxide additives (Y₂O₃, CaO, La₂O₃, CeO₂, SiO₂, TiO₂, and Fe₂O₃) were investigated as AIN sintering aids. AIN can be fully sintered at 1600°C to substantial thermal conductivity (92 W/(m·K)) using a multiple sintering aid of Y₂O₃, CaO, SiO₂, La₂O₃, and CeO₂. This lowtemperature material has small grain size (1 to 3 μm).     

Oxidation State of Chromium in CaO–Al2O3–CrOx–SiO2 Melts under Strongly Reducing Conditions at 1500°C

Equilibrium ratios Cr²⁺/Cr³⁺ of chromium oxide dissolved in CaO–chromium oxide–Al₂O₃–SiO₂ melts have been determined by analysis of samples equilibrated at 1500°C under strongly reducing conditions ( p _o2= 10^−9.56 to 10^−12.50 atm). The majority of the chromium is divalent (Cr²⁺) under these conditions and Cr²⁺/Cr³⁺ ratios at given constant oxygen pressures decrease with increasing basicity of the melts, expressed as CaO/SiO₂ ratios. In addition, Cr²⁺/Cr³⁺ ratios, at a given CaO/SiO₂ ratio, are relatively unaffected by the amount of Al₂O₃ present.     

Reaction Characteristics of Magnesia–Spinel Refractories with Cement Clinker

The adherence ability of cement clinker on magnesia–spinel refractories is investigated, using a sandwich test, at 1550°C for 30 min under a load of 5.3 kPa. Fractional factorial experiments determine that the silica ratio (SR)—SiO₂/(Al₂O₃+Fe₂O₃) and particle size of raw meal, as well as heating rate, have a significant effect on adherence ability. Microstructural analyses indicate that the adherence ability depends upon reactions between clinker and refractories at high temperature. Only spinel reacts with CaO and 3CaO·SiO₂ from clinker to form n -calcium aluminate (such as 3CaO·Al₂O₃, 12CaO·7Al₂O₃, CaO·Al₂O₃), but there is no reaction between MgO and the clinker. Fine crystalline spinel, evenly distributed in magnesia-based brick, is prone to reacting with lime-containing phases from clinker to form low melting phases and a belite-enriched zone at the clinker/brick interface. This reaction positively contributes to the high adherence on a magnesia−spinel brick. The high content of liquid in clinker with low SR accelerates reactions between spinel and clinker, while a limited reaction occurs at the brick/clinker interface with high silica.