Role of Cuspidine (3CaO.2SiO2.CaF2) in the System CaO–SiO2–CaF2

Cuspidine is a well-defined ternary compound with a stability field in the subsystem CaF₂–CaSiO₃–Ca₂SiO₄. Cuspidine is easily formed by solid-state reactions in the subsystem mentioned and is stable above its apparently congruent fusion point if heated in welded platinum containers. Above 1450° decomposition and the formation of a mixture of CaF₂ and Ca₂SiO₄ is observed. Cuspidine also is easily formed by secondary reactions in solid mixtures of the subsystem CaF₂–CaSiO₃ and in ternary mixtures of these with free SiO₂ if heated in open crucibles. The existence of double compounds of CaF₂ and CaSiO₃ is not confirmed.     

Corrosion Behaviors of Zirconia Refractory by CaO–SiO2–MgO–CaF2 Slag

In this work the corrosion behaviors of zirconia refractory (partially MgO-stabilized zirconia) was investigated in CaO–SiO₂–MgO–CaF₂ slag with varying CaF₂ content at 1873 K. To figure out the corrosion mechanism, the characteristics of present slag at high temperature were examined in terms of melting temperature and vaporization behaviors. Corrosion experiment and melting temperature measurement were carried out by heating microscope (HM) and the vaporization phenomenon was investigated by thermo gravimetry–differential scanning calorimetry. After experiment, the corroded interfaces of zirconia refractory by slag were analyzed by scanning electron microscope-energy dispersive spectroscopy and electron probe microanalysis. With an addition of CaF₂, three different layers were formed at the interface of slag and zirconia refractory. Furthermore, the corrosion behaviors of zirconia refractory were found to be continuously accelerated with an increase of CaF₂ which facilitated the dissolution of intermediate compound. On the other hand, melting temperature of CaO–SiO₂–MgO–CaF₂ slag showed no continuous decrease with an increase of CaF₂. Also, considerable vaporization of fluoride gas was occurred in high CaF₂ containing slag during HM experiment which might cause a gradual change of slag composition and also environmental pollution. From the results, present study suggested that a proper amount of CaF₂ should be added when it is used for enhancing refining capacity of slag in order not to cause any severe damage of zirconia-based refractory by slag.     

Dissolution Rate of Silicon Nitride Ceramics into Molten CaO–Al2O3–SiO2 Slags

The dissolution rates of silicon nitride (Si₃N₄) ceramics into CaOAl₂O₃SiO₂ slags were investigated by using a rotating specimen method in the temperature range of 1773–1873 K. Dissolution rates in the present study increased as the revolution speed and temperature increased and decreased as the SiO₂ content of the slags increased. The nitrogen content of the slags increased after the Si₃N₄ ceramics had been immersed into them. The slags contained two types of nitrogen ions—N³⁻ and CN^-—because a graphite crucible was used for the experiment. N³⁻ ions were confirmed in all the slags that were used in the present work; the CN^- content was much lower than that of the N³⁻ ions, except in the slag without SiO₂. Based on those results, Ficks law of diffusion was used to analyze the dissolution rates. The dissolution mechanism of the Si₃N₄ ceramics into CaO–Al₂O₃SiO₂ slags has been discussed in this paper.     

Determination of CaO–SiO2–MgO–Al2O3–CrOx Liquidus

In this work, the liquidus of synthetic CaO–SiO₂–MgO–Al₂O₃–CrO _x slags is evaluated in the industrially relevant compositional domain. Equilibrium experiments are carried out at 1500°C and partial oxygen pressure ( p _O2) 10^−11.04 atm, and at 1600°C and p _O2=10^−10.16 and 10^−9.36 atm. The studied basicities (CaO/SiO₂) are 1.2 and 0.5. Al₂O₃ levels range from 0 to 30 wt%. Oversaturated liquid is sampled and phase relations are measured with quantitative electron probe microanalysis–wavelength dispersive spectroscopy (EPMA–WDS). The results are compared with the commercially available FactSage thermodynamic databases. Qualitative agreement is always obtained. Also a good quantitative agreement is found at the higher basicity, especially for the spinel liquidus. A minor but systematic deviation can be observed for the eskolaite liquidus. At the lower basicity, the calculated phase diagram deviates strongly from the experimental results, probably due to missing ternary interactions in the database.     

Interaction of CaO–FeO–SiO2 Slags with Partially Stabilized Zirconia

Calcia- and magnesia-partially-stabilized zirconia samples were corroded under static and dynamic conditions in three slags from the CaO–FeO–SiO₂ system. Low–basicity and high–FeO slags corroded tht samples by leaching magnesia from the cubic phase in the specimen, causing its destabilization and ultimate dissolution. However, a higher–basicity slag which proved the most corrosive of the three promoted bulk dissolution of the cubic phase instead, the rate of which was controlled by the thickness of the adjacent slag boundary layer. The levels of sample corrosion both at and below the slag line are used to illustrate the effects of experimental variables, including slag composition, specimen density, and slag motion.     

The System CaO–"CaCr2O4"–CaAl2O4 in Air and under Mildly Reducing Conditions

The system CaO–chromium oxide in air is reinvestigated and the existence of intermediate phases with chromium in oxidation states >3+ (Ca₅Cr₃O₁₂, Ca₃(CrO₄)₂, and Ca₅(CrO₄)₃) confirmed. Under reducing conditions these phases are unstable. A metastable, polymorphic form of calcium chromite, δ -CaCr₂O₄, is observed. In the CaO-rich section of the CaO–Al₂O₃–Cr₂O₃ system a ternary intermediate phase, chrome-haüyne, Ca₄[(Al,Cr³⁺)₆O₁₂](Cr⁶⁺O₄), coexists with calcium chromate and calcium aluminate phases. In air, low melting temperatures are preserved in all assemblages containing calcium chromate phases. Under reducing conditions a new ternary phase, Ca₆Al₄Cr₂O₁₅, coexists with CaO, CaCr₂O₄, chrome-haüyne, and calcium aluminate phases. The influence of chromium oxide additions on the solidus temperatures of the CaO–Al₂O₃ system is insignificant.     

Crystallization of (Na2O–MgO)–CaO–Al2O3–SiO2 Glassy Systems Formulated from Waste Products

Aluminosilicate and silicate glass-ceramics were obtained from controlled devitrification of CaO–Al₂O₃–SiO₂ glassy systems starting from Spanish and Italian coal fly ash or Italian municipal incinerator slag mixed with other byproducts, such as glass cullet and dolomite. The nucleation mechanism and the crystallization kinetics were investigated by thermal, diffractometric, and microstructural measurements. Moreover, the experimentally observed devitrification and the identification of the crystalline phases formed were compared with the indications derived from Ginsberg, Raschin-Tschetveritkov, and Lebedeva diagrams used for petrological glass-ceramics. All the glasses showed a good crystallization tendency with the formation of dendritic pyroxene and acicular wollastonite together with feldspar and iron spinels starting from the surface. The activation energy values for crystallization ranging from 472 to 832 kJ ·mol⁻¹ were found to be close to those typical for aluminosilicate glasses; moreover, the possibility to vitrify and devitrify up to 100 wt% of slag and up to 40–50 wt% of ash mixed with glass cullet and dolomite makes the vitrification treatment a suitable disposal procedure.     

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.     

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.     

Viscosity Studies of System CaO–MgO–Al2O3–SiO3: IV, 60 and 65% SiO2

In this final paper of a series on viscosity in the system CaO—MgO-Al₂O₃SiO₂ data are presented for melts containing 60 and 65% SiO₂. There also are diagrammatic presentations of the systems of isokoms at intervals on planes parallel to the zero alumina, zero lime, and zero magnesia faces of the tetrahedron, the apices of which represent 100% of each of the four oxides that make up the system.     

Phase Equilibria in High-Alumina Part of the System CaO–MgO–Al2O3–SiO2

Results are presented of a study of phase equilibria among crystalline and liquid phases in the quaternary system CaO–MgO-Al₂O₃–SiO₂ at Al₂O₃ contents greater than 35%. Equilibrium diagrams shown are for the five triangular joins CaAl₂Si₂O₃-Ca₂Al₂SiO₇-MgAl₂O₄, Ca₂Al₂SiO₇-MgAl₂O₄-Al₂O₃, CaAl₂Si₂O₈-MgO-Al₂O₃, CaAl₂Si₂O₈-Mg₂SiO₄-MgAl₂O₄, and CaAl₂Si₂O₈-MgO-Mg₂SiO₄. The composition and nature of the four quaternary peritectic points and the relationships of univariant lines and primary phase volumes are discussed.     

Calcium Hexaluminate and Its Stability Relations in the System CaO–Al2O3–SiO2

By a combination of solid-state sintering and quenching experiments the validity of calcium hexaluminate as a stable phase and the extent of its primary field in the system CaO–Al₂O₃–SiO₂ have been established. The size of the primary field is considerably reduced from that suggested by earlier work. The anorthite-corundum-calcium hexaluminate invariant point has been relocated at 28.0% CaO, 39.7% Al₂O₂, and 32.3% SiO₂ and at 1405°± 5°C.     

Sintering and Crystallization of CaO–Al2O3–ZrO2–SiO2 Glasses Containing Different Amount of Al2O3

In this work several complementary techniques have been employed to carefully characterize the sintering and crystallization behavior of CaO–Al₂O₃–ZrO₂–SiO₂ glass powder compacts after different heat treatments. The research started from a new base glass 33.69 CaO–1.00 Al₂O₃–7.68 ZrO₂–55.43SiO₂ (mol%) to which 5 and 10 mol% Al₂O₃ were added. The glasses with higher amounts of alumina sintered at higher temperatures (953°C [lower amount] vs. 987°C [higher amount]). A combination of the linear shrinkage and viscosity data allowed to easily find the viscosity values corresponding to the beginning and the end of the sintering process. Anorthite and wollastonite crystals formed in the sintered samples, especially at lower temperatures. At higher temperatures, a new crystalline phase containing ZrO₂ (2CaO·4SiO₂·ZrO₂) appeared in all studied specimens.     

Immiscibility Area in the System TiO2–ZrO2–SiO2

A furnace for use in conjunction with the X-ray spectrometer was developed which was capable of heating small powdered specimens in air to temperatures as high as 1850°C. This furnace was also used for the heating and quenching of specimens in air from temperatures as high as 1850°C. An area of two liquids coexisting between 20 and 93 weight % TiO₂ above 1765°± 10°C. was found to exist in the system TiO₂–SiO₂, which is in substantial agreement with the previous work of other investigators. The area of immiscibility in the system TiO₂–SiO₂ was found to extend well into the system TiO₂–ZrO₂–SiO₂. The two liquids were found to coexist over a major portion of the TiO₂ (rutile) primary-phase area with TiO₂ (rutile) being the primary crystal beneath both liquids. The temperature of two-liquid formation in the ternary was found to fall about 80°C. with the first additions of ZrO₂ up to 3%. With larger amounts of ZrO₂ the change in the temperature of the boundary of the two-liquid area was so slight as to be within the limits of error of the temperature measurement. Primary-phase fields for TiO₂ (rutile), tetragonal ZrO₂, and ZrTiO₄ were found to exist in the system TiO₂–ZrO₂–SiO₂. SiO₂ as high cristobalite is known to exist in the system TiO₂–ZrO₂–SiO₂.     

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.     

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.     

Direct Measurement of Relative Partial Molar Enthalpy of SiO2 in SiO2–M2O (M=Li, Na, K, Cs) Binary and SiO2–CaO–Al2O3 Ternary Melts

The relative partial molar enthalpies, Δ _SiO2, of SiO₂ in SiO₂–M₂O (M = Li, Na, K and Cs) binary and SiO₂–CaO–Al₂O₃ternary melts were directly measured by drop-solution calorimetry at 1465 K and 1663 K. Δ _SiO2 changes from exothermic to endothermic as silica content increases, confirming the tendency toward immisciblity seen from activity measurements. It is concluded that Δ _SiO2 is negative due to acid-base reactions and charge-coupled substitutions when the melt is composed of fewer Q ⁴ and more Q ³ and Q ² species, but positive due to structural strain when the melt is composed of mostly Q ⁴ species. The Δ _SiO2 obtained by calorimetry is a useful measure of basicity, when comparing different alkali and alkaline earth oxides.     

Structure of Na2O–CaO–P2O5–SiO2 Glass–Ceramics with Multimodal Porosity

We have investigated the evolution of the structure of nano–macro porous CaO–Na₂O–P₂O₅–SiO₂ bioactive glass–ceramics by Fourier transform infrared (FTIR) and Raman spectroscopies, and X-ray diffraction (XRD). A controlled devitrification, followed by a chemical leaching treatment is used to produce a multimodal distribution of nano/macro pores that are expected to improve cell attachment. Data show that the leaching process removes the sodium- and calcium-containing crystalline phases that are formed during the ceramming heat treatment. The primary Si–O peaks in the infrared spectra blue shift with leaching, indicating that the sample becomes SiO₂ rich. In parallel, the fraction of nonbridging oxygen decreases. These results suggest a restructuring of the glass network far below the glass transition temperature. The stresses from leaching, capillary forces, and subsequent restructuring develop and grow, eventually producing cracks in the sample.