Slag–Portland Cement Based DSP Paste

The partial replacement of Portland cement and silica fume by ground granulated blast furnace slag in DSP cement pastes has been investigated under different curing regimens. The influence of long-term hydration at 25°C, as well as hydrothermal curing (at 80°C) and strong drying (at 200° and 400°C), on the composition and microstructures of slag–Portland cement DSP materials was investigated by nsing QXRD, TGA, MIP, and TMS-GPC methods in this study. Slag is found to be an additive improving intrinsic properties of the DSP paste. CaO/SiO₂ molar ratios of C-S-H phase in the DSP cement past have been calculated.     

Si NMR Study of the Hydration of Ca3SiO5 and ß-Ca2SiO4 in the Presence of Silica Fume

²⁹Si magic-angle spinning nuclear magnetic resonance (MASNMR) was used to study the room-temperature hydration of C₃S, ß-C₂S, and reactive ß-C₂S mixed with different amounts of silica fume (SF) that had been hydrated up to nine months and longer. The overall CaO:SiO₂ molar ratios of the mixes were 0.12, 0.20, 0.35, 0.50, and 0.80. NMR spectroscopy was used to quantify the remaining starting materials and the resulting hydration products of different species. A broad peak assigned to Q³, appearing in both the fourier transform (FT) and the cross-polarization (CP) modes, increased in intensity with increased SF content and with age. This Q³ species was attributed to two sources: (1) the surface hydroxylation of SF and (2) the cross-linking of dreierketten (chains of silicate tetrahedra arranged in a repeating three-unit conformation) in the calcium silicate hydrate (C-S-H) structure. A Q⁴ species also appeared in the CP spectra of samples with large SF additions after extended hydration and was attributed to cross-polarization by adjacent hydroxylated Q³ species at the surface of amorphous SiO₂.     

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.     

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.     

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.     

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.     

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.     

Densification of Alumina and Silica in the Presence of a Liquid Phase

Alumina and silica powders were sintered at 1250° to 1460°C in the presence of liquid phases containing CaO, A1₂O₃, and SiO₂. The data were analyzed using the equation D = K log t +C and the Arrhenius equation. The activation energy for sintering decreases with increasing amounts of liquid phase.     

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.     

Si MAS-NMR Study of Hydrated Cement Paste and Mortar Made with and without Silica Fume

This paper presents ²⁹Si MAS-NMR measurements that trace the hydration process in both cement paste and mortar specimens made from ordinary portland cement, Type I, when the cement content is replaced by 0, 10, 15, and 20 wt% of silica fume. The specimens were moist-cured for 3, 7, 14, 28, 90, and 180 days at a laboratory temperature of 21°C (69.8°F). Compressive strength for all tested specimens was also determined. The results show that the degree of hydration (Q¹+ Q²)/(Q°+ Q¹+ Q²) increased with increasing content of silica fume, especially at the early ages of 3 to 28 days. In the same manner, compressive strength results were markedly increased up to 14 days and were lowered at later ages, compared to the control mix (0 wt% silica fume).     

Incorporation of Aluminum into C–S–H Structures: From Synthesis to Nanostructural Characterization

C–A–S–H (C=CaO, A=Al₂O₃, S=SiO₂, H=H₂O in cement nomenclature) phases have been synthesized from CaO, SiO₂, and AlNaO₂. The initial CaO/SiO₂ (C/S_initial) ratios varied from 0.8 to 1.5 and the initial Al₂O₃/SiO₂ (A/S_initial) ratio was set to 0.1. Samples were characterized by X-ray diffraction and chemical analyses of their equilibrium solutions. This paper describes experiments using a low-voltage scanning transmission electron microscopy (STEM-in-SEM) imaging system that allows transmission observations in an environmental scanning electron microscope. Observations of the nanostructure were also performed by transmission electron microscopy (TEM). Two types of morphologies were clearly observed: fine fibrillar aggregates and small plates, the latter being particularly sensitive to beam damage. Despite their different appearance, both of these phases were amorphous, and the small plates were richer in aluminum. The fraction of the small plate phase increased with the C/S_initial ratio. TEM interpretations showed that C–A–S–H phases were not stable under the electron beam and high-magnification observations could significantly modify their structure. Images and chemical analyses acquired with STEM-in-SEM appeared as valuable sources of information because they offered a large observation field comparable to a transmission electron microscope and better magnification resolution than a classical scanning electron microscope.     

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.     

Some Properties of Hafnium Oxide, Hafnium Silicate, Calcium Hafnate, and Hafnium Carbide

The behavior of hafnium oxide was studied particularly in the temperature range 1500° to 18OO°C. Properties of HfO₂ at these temperatures and its reactions with ZrO₂, SiO₂, and CaO are given in terms of lattice and other physical measurements, many of which are new. Mono-clinic hafnium oxide is stable to 1700°C., which is 600° higher than the corresponding inversion temperature of zirconia. Otherwise HfO₂ closely resembles ZrO₂ (a) in its lattice dimensions and sintering behavior, (b) in forming a high-temperature tetragonal phase closely resembling tetragonal ZrO₂, (c) in forming a continuous series of solid solutions with ZrOz, (d) in forming with silica a single compound (HfO₂.SiO₂) similar to zircon, (e) in forming a carbide, (f) in uniting with up to 40% CaO to form cubic solid solutions; thereafter a compound CaO.Hf O₂ appears which is very similar to the corresponding zirconia compound.     

Chemical Interactions Between Cement and E-Glass Fibers with a CaO–BaO–SiO2–TiO2 Coating

E-glass fibers were coated with a 15CaO–15BaO–20SiO₂–50TiO₂ thin film by the sol–gel method. Mechanical and chemical tests were performed on coated and uncoated fibers in cement and cement extract solutions to investigate the interactions between cement and gel-glass film. The results show that the resistance of E-glass fibers to the alkali cement medium is enhanced by the 15CaO–15BaO–20SiO₂–50TiO₂ coating. The significant roles of TiO₂, CaO, and BaO in the protection fibers from the alkaline attack of cement are described. Some evidence is presented that the alkali corrosion of the coated fibers results in the formation of a thick and compact Ti film that suppresses further corrosion reaction.     

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.     

Titanium-Bearing Dicalcium Silicates from Rice Hull Ash: Synthesis and Properties

This work describes the synthesis of dicalcium silicates doped with titanium. Rice hull ash was used as the source of silica. Starting reagents (SiO₂, CaO, and TiO₂) were used in stoichiometric proportion in order to mantain a (Ca+Ti)/Si ratio=2. Aqueous dispersions were prepared and submitted to an ultrasonic bath for 60 min. After drying, the solids were calcined at 800°C. Chemical analyses were performed by X-ray diffraction and infrared spectroscopy. Dicalcium silicates doped with 5% of titanium were obtained. Overall, the performance of mortars containing 20% of dicalcium silicate doped with titanium was similar to mortars prepared from portland cement.     

29Si and 27Al MASNMR Study of Stratlingite

Strätlingite (2CaO·Al₂O₃·SiO₂·8H₂O) is a complex calcium aluminosilicate hydrate commonly associated with the hydration of slag-containing cements or other cements enriched in alumina. Strätlingite can coexist with the hydrogarnet solid solution [hydrogarnet (3CaO·Al₂O₃·6H₂O)-katoite (3CaO·Al₂O₃·SiO₂·4H₂O)] and calcium silicate hydrate (C-S-H). Since Strätlingite is present in many blended cements, the knowledge of strätlingite's characteristic silicate anion structure and how aluminum is accommodated by the structure is important. Phase pure Strätlingite samples have been synthesized from oxides in the presence of excess water and from metakaolinite, calcium aluminate cement, CaO, NaOH, and water. The samples were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), and thermogravimetric analysis (TGA) and then further examined using ²⁹Si, with and without cross-polarization (CP), and ²⁷Al solid-state magic angle nuclear magnetic resonance spectroscopy (MASNMR). For the most part, NMR data for these strätlingites corroborate structural information available in the literature. The aluminum atoms are both tetrahedrally and octahedrally coordinated, and the silicon atoms exist predominantly as Q₂, Q₂(1Al), and Q₂(2Al) species. The presence of alkali affects the structure of strätlingite in subtle ways, significantly reducing the Al^IV/A1^VI ratio.     

Basic Phosphate-Bonded Castables from Dolomitic-Magnesite Clinkers

Various basic refractory concretes, using dolomitic-magnesite clinkers, have been developed using phosphate binders and silica-rich additives. Three aggregate compositions with CaO/SiO₂ ratios varying from 2.01 to 2.31 wt% have been used, with two phosphate binders, differing by their chain length, and two silica additives, one colloidal, one crystalline. Maximum strengths, after curing, drying, and firing at various temperatures, have been attained by controlling the value of the CaO/(P₂O₅+ SiO₂) weight ratio of the concrete mixes close to unity. The value of this ratio has been found to be dependent upon the reactivity of the binder and the silica additive used.     

Degradation of Bioactive Polydimethylsiloxane–CaO–SiO2–TiO2 and Poly(tetramethylene oxide)–CaO–TiO2 Hybrids in a Simulated Body Fluid

It has been shown that polydimethylsiloxane (PDMS)–CaO–SiO₂–TiO₂ and poly(tetramethylene oxide) (PTMO)–CaO–TiO₂ hybrids form apatite on their surfaces in a simulated body fluid (SBF) and show mechanical properties similar to those of human cancellous bones. In the present study, changes, caused by soaking in SBF, were measured in the mechanical properties of PDMS–CaO–SiO₂–TiO₂ hybrids with different CaO and TiO₂ contents and PTMO–CaO–TiO₂ hybrids with different CaO contents. Significant decreases in the strength and strain at failure of the hybrids were observed for the PDMS–CaO–SiO₂–TiO₂ hybrids with high CaO or TiO₂ contents and PTMO–CaO–TiO₂ hybrids with a high CaO content after soaking in SBF for 4 w. This indicates that incorporation of a large amount of CaO component into the hybrids should result in the deterioration of the hybrids in the body environment.     

Thermooptic Coefficients of Soda–Lime–Silica Glasses

The thermooptic coefficients, d n /d T , of two series of soda–lime–silica glasses, 25Na₂O· x CaO·(75 – x )SiO₂ and (25 – y )Na₂O· y CaO·75SiO₂, have been measured. When CaO is substituted for SiO₂, the magnitude of d n /d T passes through a maximum negative value. When CaO is substituted for Na₂O, there is a monotonic change from negative to positive d n /d T . These effects are accounted for by the changes in relative values of the coefficient of thermal expansion and the temperature coefficient of electronic polarizability, Θ. The effect of composition on Θ is explained by the changes in density of various nonbridging and bridging oxygens in the glass.