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1.
Paste samples of tricalcium aluminate alone, with CaCl2 , with gypsum, and with gypsum and CaCl2 were hydrated for up to 6 months and the hydration products characterized by SEM, XRD, and DTA. Tricalcium aluminate hydrated initially to a hexagonal hydroaluminate phase which then changed to the cubic form; the transformation rate depended on the size and shape of the sample and on temperature. The addition of CaCl2 to tricalcium aluminate resulted in the formation of 3CaO · Al2 O3 · CaCl2 ·10H2 O and 4CaO · Al2 O3 · 13H2 O, or a solid solution of the two. The chloride retarded the formation of the cubic phase 3CaO · Al2 O3 · 6H2 O; the addition of gypsum resulted in the formation of monosulfoaluminate with a minor amount of ettringite. When chloride was added to tricalcium aluminate and gypsum, more ettringite was formed, although 3CaO · Al2 O3 · CaSO4 · 12H2 O and 3CaO · Al2 O3 · CaCl2 · 10H2 O were the main hydration products. 相似文献
2.
The morphological changes accompanying the conversion of the hexagonal CaO·Al2 O3 ·10H2 O phase to the cubic 3CaO·Al2 O3 ·6H2 O phase were studied by scanning electron microscopy. The hydration and conversion reactions were monitored by X-ray diffraction analysis. From the micrographs, it was inferred that changes in the pore structure and the presence of large cubic crystals of questionable adhesive value were probably the principal factors responsible for the loss of strength in converted calcium aluminate cement pastes. 相似文献
3.
Phase equilibria have been determined in the system CaO-Al2 O3 -H2 O in the temperature range 100° to 1000°C. under water pressures of up to 3000 atmospheres. Only three hydrated phases are formed stably in the system: Ca(OH)2 , 3CaO·Al2 O3 ·6H2 O, and 4CaO·3Al2 O3 -3H2 O. Pressure-temperature curves delineating the equilibrium decomposition of each of these phases have been determined, and some ther-mochemical data have been deduced therefrom. It has been established that both the compounds CaO·Al2 O3 and 3CaO·Al2 O3 have a minimum temperature of stability which is above 1000°C. The relevance of the new data to some aspects of cement chemistry is discussed. 相似文献
4.
ELSE BREVAL 《Journal of the American Ceramic Society》1979,62(7-8):395-398
Liquid hydration and water-vapor hydration of 3CaO·Al2 O3 , were studied. Variable parameters were hydration time, temperature, relative humidity, and amount of gypsum. The hydration products (gel, ettringite, hexagonal hydrates, and 3CaO·Al2 O3 ·6H2 O) were studied by electron microscopy, X-ray diffractometry, and thermal analysis. A reaction scheme is proposed. The degree of water-vapor hydration influenced the sequence of the subsequent liquid hydration which, however, was independent of the composition of the water-vapor hydration products. Below a critical degree of water-vapor hydration (≊3% combined water) the reaction with liquid water occurred as if no water-vapor hydration had taken place. Above this value the reaction gave hydration products suggesting a change of the 3CaO·Al2 O3 reactivity. A possible correlation with the retardation of strength development of prehydrated cement is suggested. 相似文献
5.
Stephen Kwan Judith LaRosa Michael W. Grutzeck 《Journal of the American Ceramic Society》1995,78(7):1921-1926
Strätlingite (2CaO·Al2 O3 ·SiO2 ·8H2 O) 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·Al2 O3 ·6H2 O)-katoite (3CaO·Al2 O3 ·SiO2 ·4H2 O)] 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 29 Si, with and without cross-polarization (CP), and 27 Al 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 AlIV /A1VI ratio. 相似文献
6.
Nakshatra B. Singh Awadhesh K. Singh Shashi Prabha Singh 《Journal of the American Ceramic Society》1990,73(10):3063-3068
Hydration occurring in the system Ca3 Al2 O6 –CaSO4 · 2H2 O–Ca(OH)2 –H2 O has been studied at different temperatures and it was found that the reactions are diffusion controlled. The kinetic data obeyed Jander's equation and the rate of reaction increased with increasing temperature. X-ray diffraction studies and calorimetric measurements show that when gypsum is consumed, ettringite is converted into monosulfate. The rate of this conversion also increased with the increasing temperature and decreased in the presence of citric acid. Spectroscopic studies showed that there was some interaction between citric acid and the cement and that the product of hydration is of colloidal nature. Zeta potential measurements show that retardation of Ca3 Al2 O6 hydration in the presence of gypsum and Ca(OH)2 is not due to SO2− 4 adsorption. Electrical conductivity and thermoelectric potential measurements of solid Ca3 Al2 O6 show that Ca3 Al2 O6 is an n -type semiconductor and contains defects. The retardation of Ca3 Al2 O6 may be due to poisoning of reaction sites by gypsum and Ca(OH)2. 相似文献
7.
The formation of ettringite (3CaO·Al2 O3 ·3CaSO4 ·32H2 O) from monosulfate (3CaO·Al2 O3 ·CaSO4 ·12H2 O) and gypsum (CaSO4 ·2H2 O) 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. 相似文献
8.
Calcium hexa-aluminate (CaO·6Al2 O3 ) has been prepared from calcium nitrate and aluminum sulfate solutions in the temperature range of 1000°–1400°C. A 0.3 mol/L solution of aluminum sulfate was prepared, and calcium nitrate was dissolved in it in a ratio that produced 6 mol of Al2 (SO4 )3 ·16H2 O for each mole of Ca(NO3 )2 ·4H2 O. It was dried over a hot magnetic stirrer at ∼70°C and fired at 1000°–1400°C for 30–360 min. The phases formed were determined by XRD. It was observed that CaO·Al2 O3 and CaO·2Al2 O3 were also formed as reaction intermediates in the reaction mix of CaO·6Al2 O3 . The kinetics of the formation of CaO·6Al2 O3 have been studied using the phase-boundary-controlled equation 1 − (1 − x )1/3 = K log t and the Arrhenius plot. The activation energy for the low-temperature synthesis of CaO·6Al2 O3 was 40 kJ/mol. 相似文献
9.
The phase diagram for the ternary system MgO─P2 O5 ─H2 O at 25°C has been constructed. The magnesium phosphates represented are Mg(H2 PO4 )2 · n H2 O ( n = 4, 2, 0), MgHPO4 ·3H2 O, and Mg3 (PO4 )2 · m H2 O ( m = 8, 22). Because of the large differences in the solubilities of these compounds, the technique which involves plotting the mole fractions of MgO and P2 O5 as their 10th roots has been employed. With the exception of MgHPO4 ·3H2 O, the magnesium phosphates are incongruently soluble. Because incongruency is associated with a peritectic-like reaction, the phase Mg2 (PO4 )3 · 8H2 O persists metastably for an extended period. 相似文献
10.
F. G. BUTTLER L. S. DENT GLASSER H. F. W. TAYLOR 《Journal of the American Ceramic Society》1959,42(3):121-126
Single-crystal X-ray and electron-diffraction studies show the existence in one polymorph of 4CaO.Al2 O3 . 13H2 O of a hexagonal structural element with α= 5.74 a.u., c = 7.92 a. u. and atomic contents Ca2 (OH)7 - 3H2 O. These structural elements are stacked in a complex way and there are probably two or more poly-types as in SiC or ZnS. Hydrocalumite is closely related to 4CaO.A12 O3 .13H2 O, from which it is derived by substitution of CO3 2- for 20H- + 3H2 O once in every eight structural elements; similar substitutions explain the existence of compounds of the types 3CaO Al2 O3 .Ca Y 2 - xH2 O and 3CaO Al2 O3 Ca Y xH2 O. On dehydration, 4CaO.Al2 O3 .13H2 O first loses molecular water and undergoes stacking changes and shrinkage along c. At 150° to 250°C., Ca(OH)2 and 4CaO.3Al2 O3 .3H2 O are formed and, by 1000°C., CaO and 12CaO.7Al2 O8 . The dehydration of hydrocalumite follows a similar course, but no 4CaO.3Al2 O3 .3H2 O is formed. 相似文献
11.
Yoshikazu Suzuki Masahiro Tsukatsune Susumu Yoshikawa Peter E. D. Morgan 《Journal of the American Ceramic Society》2005,88(11):3283-3286
Porous Al2 O3 /20 vol% LaPO4 and Al2 O3 /20 vol% CePO4 composites with very narrow pore-size distribution at around 200 nm have been successfully synthesized by reactive sintering at 1100°C for 2 h from RE2 (CO3 )3 · x H2 O (RE = La or Ce), Al(H2 PO4 )3 and Al2 O3 with LiF additive. Similar to the previously reported UPC-3Ds (uniformly porous composites with a three-dimensional network structure, e.g. CaZrO3 /MgO system), decomposed gases in the starting materials formed a homogeneous open porous structure with a porosity of ∼40%. X-ray diffraction, 31 P magic-angle spinning nuclear magnetic resonance, scanning electron microscopy, and mercury porosimetry revealed the structure of the porous composites. 相似文献
12.
SHIGEKAZU MINAGAWA 《Journal of the American Ceramic Society》1972,55(2):77-80
The kinetics of the growth of Al2 O3 whiskers by the reaction of Al with a trace amount of H2 O in an H2 atmosphere were studied. The activation energy in the region of constant growth rate was ∼77 kcal mol−1 . This activation energy value, in the light of thermodynamic calculations and other theoretical considerations, suggests that the rate-determining step in the growth of these whiskers is the dissociation of H2 O molecules on the surface of Al2 O3 . 相似文献
13.
Kinetics of the Early Hydration of Tricalcium Aluminate in Solutions Containing Calcium Sulfate 总被引:1,自引:0,他引:1
PAUL WENCIL BROWN LAWRENCE O. LIBERMAN GEOFFREY FROHNSDORFF 《Journal of the American Ceramic Society》1984,67(12):793-795
The rates of reaction of 3CaO. Al2 O3 , 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·Al2 O3 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·Al2 O3 · n H2 O in addition to ettringite. 相似文献
14.
Debao Zhang Baoyu Chen Zhuping Liu Shunguang Li Lili Hu 《Journal of the American Ceramic Society》2004,87(12):2228-2231
Er3+ -doped sodium lanthanum aluminosilicate glasses with compositions of (90− x )(0.7SiO2 ·0.3Al2 O3 )· x Na2 O·8.2La2 O3 · 0.6Er2 O3 ·0.2Yb2 O3 ·1Sb2 O3 (in mol%) ( x = 12, 20, 24, 40, 60 mol%) were prepared and their spectroscopic properties were investigated. Judd–Ofelt analysis was used to calculate spectroscopic properties of all glasses. The Judd–Ofelt intensity parameter Ω t ( t = 2, 4, 6) decreases with increasing Na2 O. Ω2 decreases rapidly with increasing Na2 O while Ω4 and Ω6 decrease slowly. Both the fluorescent lifetime and the radiative transition rate increase with increasing Na2 O. Fluorescence spectra of the 4 I 13/2 to 4 I 15/2 transition have been measured and the change with Na2 O content is discussed. It is found that the full width at half-maximum decreases with increasing Na2 O. 相似文献
15.
R. F. FELDMAN V. S. RAMACHANDRAN P. J. SEREDA 《Journal of the American Ceramic Society》1965,48(1):25-30
The influence of CaCO3 on the hydration of 3CaO Al2 O3 containing about 90% C3 A is studied with compacts of their mixtures proportioned to 0, 2.5, 10, 20, and 50 wt% CaCO3 . The compacts are exposed to H2 O in liquid and in vapor phase, the attendant expansion being measured as a function of time. Differential thermal analysis, infrared absorption, and X–ray diffraction are used in conjunction with this technique. It is shown that the hydration reaction of 3 CaO · Al2 O3 is suppressed by CaCO3 additions and that this is due primarily to the formation of the low form of calcium carboaluminate on the surface of the C3 A grains. Expansion measurements of the compacts during the reactions show that this technique indicates the progress of hydration and detects the formation of the carboaluminate at an early stage of the reaction. Using the same technique, a study at 50% relative humidity provides the basis for the conclusion that C3 A reacts with CaCO3 under these conditions by a direct mechanism. 相似文献
16.
Koji Tsukuma 《Journal of the American Ceramic Society》2000,83(12):3219-3221
Composites of β-Ce2 O3 ·11Al2 O3 and tetragonal ZrO2 were fabricated by a reductive atmosphere sintering of mixed powders of CeO2 , ZrO2 (2 mol% Y2 O3 ), and Al2 O3 . The composites had microstructures composed of elongated grains of β-Ce2 O3 ·11Al2 O3 in a Y-TZP matrix. The β-Ce2 O3 ·11Al2 O3 decomposed to α-Al2 O3 and CeO2 by annealing at 1500°C for 1 h in oxygen. The elongated single grain of β-Ce2 O3 ·11Al2 O3 divided into several grains of α-Al2 O3 and ZrO2 doped with Y2 O3 and CeO2 . High-temperature bending strength of the oxygen-annealed α-Al2 O3 composite was comparable to the β-Ce2 O3 ·11Al2 O3 composite before annealing. 相似文献
17.
CECIL M. JONES II 《Journal of the American Ceramic Society》1971,54(7):347-349
A technique for growing α-Al2 O3 crystals is described in which Na2 O·11Al2 O3 is dissolved in a liquid of composition Na2 O·4TiO2 ·3Al2 O3 . Alpha Al2 O3 is precipitated as Na2 O evaporates from the system; Na2 O·11Al2 O3 serves as a source of Al2 O3 , and Na2 O in the liquid. The content of solids in the mixture is always such that it does not melt completely. The size of the α-Al2 O3 crystals grown is related to the Na2 O content of the composition. Crystals as large as 4000 by 3000 μm in the α-axis direction and 500 μm in the c -axis direction have been grown. 相似文献
18.
Masayuki Nogami Naoya Hayakawa Naoya Sugioka Yoshihiro Abe 《Journal of the American Ceramic Society》1996,79(5):1257-1261
Samarium ions (Sm2+ ) incorporated into aluminosilicate glasses by a sol-gel process showed persistent spectral hole burning at room temperature. Gels of the system Na2 O-Al2 O3 SiO2 synthesized by the hydrolysis of Si(OC2 H5 )4 , Al(OC4 H9 )3 , CH3 COONa, and SmCl3 ·6H2 O were heated in air at 500°C, then reacted with H2 gas to form Sm2+ ions. Whereas Al3+ ions effectively dispersed the Sm3+ ions in the glass structure, Na+ ions were not effective. The Al2 O3 -SiO2 glasses proved appropriate for reacting the Sm3+ ions with H2 gas and exhibited the intense photoluminescence of Sm2+ ions. The reaction of Sm3+ ions with H2 in the Al2 O2 -SiO2 glasses was determined by first-order kinetics, and the activation energy equaled 95 kJ/mol. At 800°C, the maximum photoluminescence of the Sm2+ ions was achieved within 20 min. 相似文献
19.
Polycrystalline Al2 O3 was chemically vapor-deposited onto sintered Al2 O3 substrates by reaction of AlCl3 with (1) H2 O, (2) CO:H2 , and (3) O2 at 1000° and 1500°C and 0.5 and 5.0 torr. Although the thermodynamics of all these reactions predict the formation of solid Al2 O3 , the deposition rate of the first reaction was considerably greater than that of the second. The third reaction was so slow that no measurable deposit was formed in 6 h at 1500°C. Formation of dense deposits of α-Al2 O3 was favored by increasing temperature and decreasing pressure. Microstructural examination of the dense deposits showed long columnar grains, the largest of which extended through the deposit from the substrate to the surface. 相似文献
20.
Bengt Hallstedt 《Journal of the American Ceramic Society》1995,78(1):193-198
The system CaO–MgO–Al3 O3 has been assessed with the Calphad technique using a computerized optimization procedure called parrot . The rather meager experimental information, mainly on liquidus relations, is described reasonably well, but the lack of data, especially on solid-phase relations, implies that the present assessment should be regarded as provisional. The system contains one stable ternary phase with the stoichiometry 3CaO·2Al2 O3 ·MgO. 相似文献