Hydration Products and Reactivity of Blast-Furnace Slag Activated by Various Alkalis

Pastes of blast-furnace slag were cured for up to 90 d using sodium silicate (waterglass), NaOH, and three different mixtures of Na₂CO₃–Na₂SO₄–Ca(OH)₂ to activate reactions. The highest slag reactivity was observed for NaOH activation and the least for waterglass, although nonevaporable water indicated similar amounts of hydration products formed. The main hydration products found using X-ray diffractometry in all systems were calcium silicate hydrate (C-S-H) and a hydrotalcite-type phase. Microanalysis was performed on pastes activated using 50% Na₂CO₃·25% Na₂SO₄·25% Ca(OH)₂, NaOH, and waterglass; the chemical composition of the C-S-H in the waterglass case was different relative to the other two alkalis. For all alkaline agents used, the C-S-H seemed finely intermixed with a hydrotalcite-type phase of Mg/Al = 1.82, on average.     

Phase Transformation during Plasma Spraying of Hydroxyapatite–10-wt%-Zirconia Composite Coating

This study aims to explore phase transformation in plasma-sprayed hydroxyapatite (HA) + 10 wt% ZrO₂–8-mol%-Y₂O₃composite coating, using separately prepared HA and ZrO₂–8-mol%-Y₂O₃coatings as a control. Changes in the phase and chemistry of the coatings are characterized by X-ray diffractometry, with lattice-constant measurement (Cohen's method), and by transmission electron microscopy. Experimental results show evidence of diffusion, in the liquid state, of calcium ions from the HA matrix into the ZrO₂. This behavior causes the formation of the following structural features in the composite coating: (i) a CaO-doped ZrO₂solid solution (ZrO₂–7.7 mol% Y₂O₃–4.4 mol% CaO); (ii) a mixture of ZrO₂and CaZrO₃having a crystal-orientation relationship; (iii) an amorphous phase containing elements of calcium, phosphorus, zirconium, and yttrium; and (iv) a remaining CaO-poor HA matrix (Ca_{10− x} (HPO₄) _x (PO₄)_{6− x} (OH)_{2− x} ; x = 0.06). Rationales for the greatly decreased impurity phases of CaO and Ca₄P₂O₉found in the composite coating are discussed.     

Nanocrystalline Yttria-Stabilized Zirconia Fibers from Plant Fibers and their Polymer Composites

Nanocrystalline zirconia–8-mol% yttria (yttria-stabilized zirconia (YSZ): ZrO₂–8-m% Y₂O₃) fibers have been prepared from aqueous poly vinyl alcohol (PVA)–zirconium oxy nitrate solution and jute (plant fiber). Soluble Zr and Y ions in PVA solution formed a uniform coating on the surface of jute once it dried completely. Slow hydrolysis of zirconium ion with ammonium hydroxide deposited zirconium hydroxide on the jute surface. Decomposition of the dried zirconium hydroxide-coated jute at high temperature (1200°C/2 h) resulted in the formation of single-phase, nanocrystalline cubic-YSZ with the corresponding average X-ray crystallite size 30–35 nm. Heat-treated fibers have been characterized by X-ray diffraction and scanning electron microscopy. We also prepared polymer composites by incorporating chopped, ground YSZ fibers into epoxy matrix and investigated polymer/fiber interface by transmission electron microscopy analysis.     

The System Na2O-CaO-SiO2-H2O

A portion of the quaternary phase diagram for Na₂O-CaO-SiO₂-H₂O has been constructed. Plotting concentrations as their 10th roots allows compounds having solubilities which differ by several orders of magnitude to be represented on a single diagram. The compositional relationships among sodium-substituted calcium silicate hydrate, calcium-substituted sodium silicate hydrate, calcium bydroxide, a quaternary compound of approximate composition 0.25Na₂O · CaO · SiO₂· 3H₂O, sodium hydroxide monohydrate, and miscellaneous sodium silicate hydrates are presented. The quaternary diagram constructed shows the quaternary compound to exist in equilibrium with sodium-substituted calcium silicate hydrate and calcium hydroxide. Conditions in concrete pore solutions which favor the formation of this quaternary compound may also favor the occurrence of the alkali-silica reaction.     

Kinetics of the Early Hydration of Tricalcium Aluminate in Solutions Containing Calcium Sulfate

The rates of reaction of 3CaO. Al₂O₃, in sulfate-containing solutions of three compositions were investigated. It was observed that the rates of calcium and sulfate uptake decreased with increasing calcium hydroxide concentration. In a further experiment using a calcium sulfate solution, which also contained NaOH, it was established that the kinetics of calcium sulfoaluminate hydrate formation are strongly dependent on the hydroxyl ion concentration. The rate of sulfate ion consumption per unit surface area of 3CaO·Al₂O₃ was observed to be constant during the period in which a calcium sulfoaluminate hydrate is a reaction product. The ratio of calcium-to-sulfate ions consumed in the hydration reactions investigated exceeded unity suggesting the formation of 4CaO·Al₂O₃· n H₂O in addition to ettringite.     

Phase Relations in the System NaF-CaF2-NaAlSiO4-CaAl2Si2O8

The phase diagram of the pseudoternary reciprocal system NaF–CaF₂–NaAlSiO₄–CaAl₂Si₂O₈ is reported in this paper. The phase relations in the system have been investigated by differential thermal analysis, quenching melts, X-ray diffractometry, and optical and electron microscopies. The stable diagonal CaF₂–NaAlSiO₄ divides the system in two pseudoternary systems. The solidus temperatures in the two subsystems NaF–CaF₂–NaAlSiO₄ and CaF₂–NaAlSiO₄–CaAl₂Si₂O₈ are 805°± 2°C and 1095°± 4°C, respectively. An extensive region of liquid–liquid immiscibility is evident in the NaF–CaF₂–NaAlSiO₄ subsystem. The compositions of the two liquids fall outside the compositional surface NaF–CaF₂–NaAlSiO₄–CaAl₂Si₂O₈, but only a small deviation from the ternary behavior is observed.     

Novel Preparation Method of Hydroxyapatite Fibers

A novel method for preparing calcium hydroxyapatite (Ca₁₀(PO₄)₆(OH)₂: HAp) fibers has been developed. HAp fibers can be prepared successfully by heating a compact consisting of calcium metaphosphate (ß-Ca(PO₃)₂) fibers with Ca(OH)₂ particles in air at 1000°C and subsequently treating the resultant compact with dilute aqueous HCl solution. The ß-Ca(PO₃)₂ fibers and the Ca(OH)₂ in the compact were converted into fibrous HAp and CaO phases by the heating, and the CaO phase was removed by acid-leaching. HAp fibers obtained in the present work were 40-150 µm in length and 2-10 µm in diameter. The fibers had almost the same dimensions as those of the ß-Ca(PO₃)₂ fibers.     

Use of CsCl to Enhance the Glass Stability Range of Tellurite Glasses for Er3+-Doped Optical Fiber Drawing

Tellurite glasses are important as a host of Er³⁺ ions because of their good solubility and because they present broadband optical gain compared with Er³⁺-doped silica, with the potential to increase the bandwidth of communication systems. However, the small glass stability range (GSR) of tellurite glasses compromises the quality of the optical fibers. We show that the addition of CsCl to tellurite glasses can increase their GSR, making it easier to draw good-quality optical fibers. CsCl acts like a network modifier in glass systems, weakening the network by forming Te–Cl bonds. We show that the thermal expansion coefficient mismatch is in the right direction for optical fiber fabrication purposes and that the Bi₂O₃ content can be used to control the refractive index of clad and core glasses. Single-mode and multi-mode Er³⁺-doped optical fibers were produced by the rod-in-tube method using highly homogeneous TeO₂–ZnO–Li₂O–Bi₂O₃–CsCl glasses.     

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.     

Fluoride Model Systems: II, The Binary Systems CaF2–BeF2, MgF2–BeF2, and LiF–MgF2

Data obtained by quenching, thermal, and high-temperature X-ray techniques are presented for the three binary systems CaF₂–BeF₂, MgF₂–BeF₂, and LiF–MgF₂. The systems CaF₂–BeF₂ and MgF₂–BeF₂ are presented as weakened models of the systems ZrO₂–SiO₂ and TiO₂–SiO₂, respectively. The compound CaBeF₄ is a model of ZrSiO₄ (zircon). New data obtained for the system LiF–MgF₂ explain many discrepancies among the results of previous authors. Solid solution is almost complete between LiF and MgF₂ at elevated temperatures, but a small gap occurs at the eutectic (735°C.) with extensive exsolution at lower temperatures.     

Effects of Doping Trivalent Ions in Bismuth Borate Glasses

Bismuth borate glasses from the system: 40Bi₂O₃–59B₂O₃–1Tv₂O₃ (where Tv=Al, Y, Nd, Sm, and Eu) and three glasses of composition: 40Bi₂O₃–60B₂O₃, 37.5Bi₂O₃–62.5B₂O₃ and 38Bi₂O₃–60B₂O₃–2Al₂O₃ were prepared by melt quenching and characterized by density, UV-visible absorption spectroscopy and differential thermal analysis (DTA) studies. Bismuth borate glasses exhibit a very strong optical absorption band just below their absorption edge. Glasses were devitrified by heat treatment at temperatures above their glass transition temperatures and the crystalline phases produced in them were characterized by Fourier transform infrared (FTIR) absorption spectroscopy and X-ray diffraction (XRD). Bi₃B₅O₁₂ was found to be the most abundant phase in all devitrified samples. DTA studies on glasses and FTIR and XRD analysis on crystallized samples revealed that very small amounts of trivalent ion doping causes significant changes in the devitrification properties of bismuth borate glasses; rare-earth ions promote the formation of metastable BiBO₃–I and BiBO₃–II phases during glass crystallization.     

Scintillation from Eu2+ in Nanocrystallized Glass

A Eu²⁺-doped SiO₂–Al₂O₃–CaO–CaF₂ glass was prepared and converted into a transparent glass ceramic by heat treatment. The crystalline phase and its size were determined by X-ray diffraction and a transmission electron microscopy. The scintillation of Eu²⁺ ions in both glass and ceramic under X-ray excitation was investigated and compared with that in a single-crystal scintillator.     

Properties and Network Constitution of rf-Sputtered Amorphous Films in the System Silicon Dioxide–Aluminum Orthophosphate

Amorphous films in the system SiO₂–AlPO₄ were prepared by means of the rf-sputtering method, and their physical properties, such as density, refractive index, and temperature coefficient of Young's modulus, and infrared spectra were measured. Also, the K α X-ray emission spectra of silicon and aluminum were measured in order to investigate the coordination state of these cations in the amorphous films. The density and the refractive index were close to those of amorphous SiO₂ and AlPO₄ and the compositional dependence showed a small deviation from linearity. The temperature coefficients of Young's modulus were positive for all of the samples. The infrared absorption spectra of all of the samples were similar to those of SiO₂ glass and amorphous AlPO₄ film, and there was no evidence of the presence of P═O bonds. The coordination states of silicon and aluminum ions in the present amorphous films were the same as those in fused silica and AlPO₄ crystal, respectively. The results of the properties, infrared absorption spectra, and X-ray emission spectra suggest that SiO₄ tetrahedrons and AlO₄–PO₄ connecting tetrahedral dimers constitute the network of the present amorphous films. A small deviation of the physical properties from an additive rule was thought to result from the difference in the bond character between the newly formed Si–O–Al and Si–O–P bonds and the bonds in the end members, Si–O–Si and Al–O–P.     

Densification and Phase Transformation During Pressureless Sintering of Nanocrystalline ZrO2–Y2O3–CuO Ternary System

ZrO₂–Y₂O₃–CuO nanocrystalline powders have been synthesized using a chemical coprecipitation method. Nano-powders were compacted uniaxially and densified in a muffle furnace. Densification studies show that the presence of CuO accelerates the densification process of ZrO₂(3Y). A fully dense (>96%) pellet of ZrO₂(3Y)/5 mol% CuO was obtained after sintering at 900°C, with a very small grain size of 44 nm calculated by X-ray line broadening.     

Formation of Ettringite from Monosubstituted Calcium Sulfoaluminate Hydrate and Gypsum

The formation of ettringite (3CaO·Al₂O₃·3CaSO₄·32H₂O) from monosulfate (3CaO·Al₂O₃·CaSO₄·12H₂O) and gypsum (CaSO₄·2H₂O) was investigated by isothermal calorimetry and X-ray diffraction (XRD) analyses. Hydration was carried out at constant temperatures from 30° to 80°C using deionized water and 0.2 M , 0.5 M , and 1.0 M sodium hydroxide (NaOH) solutions. Ettringite was found to be the dominant crystalline phase over the entire temperature range and at all sodium hydroxide concentrations. A sodium-substituted monosulfate phase was formed as a hydration product in the 1.0 M sodium hydroxide solution regardless of temperature. XRD and calorimetry demonstrate that hydration in increasing sodium hydroxide concentrations decreases the amount of ettringite formed and retards the rate of reaction. The apparent activation energy for the conversion of the monosulfate/gypsum mixture to ettringite was observed to vary depending on the sodium hydroxide concentration. Ettringite formation was observed to depend upon the concentration of calcium in solution; thus the formation of calcium hydroxide and sodium-substituted monosulfate phase competes with ettringite formation.     

Isothermal Section of a Cu2O–Al2O3–SiO2 Pseudo-Ternary System at 1150°C in Air

In this study, the isothermal section of a Cu₂O–Al₂O₃–SiO₂ pseudo-ternary phase diagram at 1150°C was analyzed by means of a scanning electronic microscope and powder X-ray diffraction of the quenched samples qualitatively, and the compositions of the tie-points of the tie-planes as well as their regions were determined by in situ high-temperature quantitative X-ray diffraction analysis and energy-dispersive X-ray spectroscopy. Then, the isothermal section of the Cu₂O–Al₂O₃–SiO₂ pseudo-ternary phase diagram at 1150°C was constructed; it was found that the isothermal section is composed of two single liquid-phase regions, five two-phase regions, and six three-phase regions.     

A Study of the Phase Relations of ZrO2–TiO2 and ZrO2–TiO2–SiO2

The phase relations of the systems ZrO₂–TiO₂ and ZrO₂–TiO₂–SiO₂ were investigated. X-ray diffraction techniques served as the principal means of analysis. The binary system ZrO₂–TiO₂ was found to be one of partial solid solutions with no intermediate compounds. A eutectic point was found to exist at 50 to 55 weight % ZrO₂ and 1600°C. A preliminary investigation of the ternary system ZrO₂–TiO₂–SiO₂, although not extensive, resulted in a better understanding of this system, with a fairly accurate location of some of its boundary lines. A eutectic point was located at 2% ZrO₂, 10% TiO₂, and 88% SiO₂ at approximately 1500°C.     

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.     

Thermal Expansion Characteristics of Alumina–Magnesia and Alumina–Spinel Castables in the Temperature Range 800°–1650°C

The thermal expansion of Al₂O₃–MgO castables containing 5.5 wt% MgO and 1.36 wt% CaO and Al₂O₃–spinel castables containing 20 wt% spinel having 95 wt% Al₂O₃ and 1.7 wt% CaO was measured in the temperature range of 800–1650°C by dilatometry. A sharp increase in expansion from around 1425° to 1525°C, followed by a sharp decrease with further increasing temperature, is characteristic of Al₂O₃–MgO castables. The sharp increase in expansion is believed to be caused by the bond linkage between the CA₆ and spinel grains in the bonding matrix, while the sharp decrease is apparently related to liquid-phase sintering. The sharp increase and decrease in expansion were not observed in Al₂O₃–spinel castables because of the much lower MgO (around 1 wt% MgO) and impurity contents. The magnitude of thermal expansion of calcium aluminate bonded castables containing self-forming or preforming spinels or both is dictated by the MgO content of the castables.     

Direct Formation of Mg–Al-Layered Double-Hydroxide Films on Glass Substrate by the Sol–Gel Method With Hot Water Treatment

Amorphous Al₂O₃–MgO thin films with an Mg/Al ratio of unity were prepared on glass substrates by the sol–gel method with a heat treatment at 300°C for 30 min. By immersing the films in water containing sodium hydroxide (pH 10–13) at 100°C, nano-crystals of Mg–Al-layered double hydroxide (LDH) with a hexagonal structure, which is called hydrotalcite and the most basic composition of LDH, were precipitated on the amorphous Al₂O₃–MgO films. The maximum amount of Mg–Al nanocrystals was obtained when the film was immersed in basic solution of pH 12.