Microstructural and Microchemical Characterization of a Calcium Aluminate—Polymer Composite (MDF Cement)

The microstructure of a macrodefect-free (MDF) cement has been characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), and high-resolution electron microscopy (HREM). The microchemistry of ultramicrotomed samples has been studied by energy dispersive spectrometry (EDS) and parallel electron energy loss spectrometry (PEELS). MDF cement consists of CaAl₂O₄ and CaAl₄O₇ grains randomly distributed in a polymer matrix. The ceramic/polymer interface contains an amorphous interphase inside of which are distributed very fine crystallites of the metastable hydration product Ca₂Al₂O₅·8H₂O. PEELS analyses of the interphase revealed the presence of carbon, indicating that Ca₂Al₂O₅·8H₂O was most likely stabilized by the intercalation of polymeric chains into its basal interlayers. The polymer phase preferably cross-links with Al. In situ environmental cell electron microscopy showed that moisture uptake of MDF cements occurred by polymer swelling and interphase dissolution. The role of the interfacial interphase in dry and wet mechanical properties is discussed.     

Low-Temperature Synthesis of Hexagonal Anorthite via Hydrothermal Processing

Hexagonal anorthite (CaAl₂Si₂O₈) has been prepared by hydrothermal processing of monocalcium aluminate and quartz at temperatures as low as 200°C. The successful development of this phase is dependent upon several processing parameters, including the hydration of the calcium aluminate precursor material to the hydrogarnet phase (Ca₃Al₂O₆·6H₂O) prior to hydrothermal treatment and the use of quartz as opposed to amorphous sources of SiO₂. Quartz has partial solubility in the hydrogarnet lattice for additions up to 40 wt%. Increased SiO₂ substitution has been shown to reduce the conversion of hydrogarnet to Ca₄Al₆O₁₃·3H₂O, thereby increasing its thermal stability and improving its strength characteristics at temperatures greater than 200°C. Quartz additions greater than 43 wt% lead to the formation of CaAl₂Si₂O₈ as the sole reaction product. The moderate temperatures involved in forming this anhydrous material are an order of magnitude lower than those necessary to form this phase by melt crystallization, making it a true chemically bonded ceramic. The reaction can form a bonded matrix with strengths up to 40000 psi (280 MPa). Strengths are limited due to density changes during anorthite formation, but the matrix is thermally stable up to 1000°C.     

Hydration Study of the System Ca3Al2O6–CaSO4· 2H2O–Ca(OH)2–H2O with and without Citric Acid

Hydration occurring in the system Ca₃Al₂O₆–CaSO₄· 2H₂O–Ca(OH)₂–H₂O 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 Ca₃Al₂O₆ 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 Ca₃Al₂O₆ show that Ca₃Al₂O₆ is an n -type semiconductor and contains defects. The retardation of Ca₃Al₂O₆ may be due to poisoning of reaction sites by gypsum and Ca(OH)_2.     

Encapsulation of Sn(II) and Sn(IV) Chlorides in Composite Cements

The hydration of two high replacement composite cements (3:1 blast furnace slag:ordinary Portland cement (BFS:OPC), and 3:1 pulverized fuel ash:OPC (PFA:OPC)) with the addition of both SnCl₂ and SnCl₄ has been investigated and the results from X-ray diffraction (XRD) and scanning electron microscopy (SEM) with energy-dispersive spectroscopy (EDS) are presented. Adding 5% or 1% SnCl₂·2H₂O or SnCl₄·5H₂O to the mix water resulted in the formation of Friedel's salt, Ca₃Al₂O₆.CaCl₂·10H₂O, and calcium hydroxo-stannate CaSn(OH)₆, which also involved the consumption of calcium hydroxide. After 90 days hydration at lower levels of addition (i.e., 1%) there was no longer evidence for CaSn(OH)₆, indicating that it too had been consumed in the pozzolanic reaction due to the lack of calcium hydroxide present. Results from SEM and EDS showed that bright regions between the BFS or PFA grains were tin containing and they were incorporated into the hydrated cement matrix. The tin was, therefore, localized rather than spread throughout and intimately incorporated into the microstructure.     

Synthesis and Characterization of (Ce0.67Tb0.33)MnxMg1−xAl11O19 Phosphors Derived by Sol–Gel Processing

A (Ce_0.67Tb_0.33)Mn _x Mg_{1− x} Al₁₁O₁₉ phosphor powder was synthesized, using a simple sol–gel process, by mixing citric acid with CeO₂, Tb₄O₇, Al(NO₃)₃·9H₂O, Mg(OH)₂·4MgCO₃·6H₂O, and Mn(CH₃COO)₂. The phosphor crystallized completely at 1200°C, and the phosphor particle size was between 1 and 5 μm. The excitation spectrum was characteristic of Ce³⁺, while the emission spectrum was composed of lines from Tb³⁺ and Mn²⁺. The Mn²⁺ gave a green fluorescence band, and concentration quenching occurred when x > 0.10. The luminescent properties of the phosphor were explained by a configurational coordinate model.     

Synthesis of Mesoporous Needle-Shaped Ytterbium Oxide Crystals by Solvothermal Treatment of Ytterbium Chloride

The reaction of rare-earth (RE; Y, Er, and Yb) chloride hydrates in 1,4-butanediol at 300°C for 2 h gave mixtures of RE(OH)₂Cl and RE₂O₃· x H₂O, and the products were composed of irregularly shaped particles. A prolonged reaction (10 h) yielded a mixture of RE(OH)₂Cl and RE₂O₃· x H₂O for Er or Y, but phase-pure RE₂O₃· x H₂O was obtained for Yb. The product for Yb comprised needle-shaped single crystals of Yb₂O₃· x H₂O with a width of 0.2–0.6 μm and a length of 5–15 μm. The Yb₂O₃· x H₂O phase decomposed to Yb₂O₃ at 350°–500°C, preserving the needle-shaped morphology; this was maintained even after calcination at 1100°C. Single crystals of Yb₂O₃ obtained by the calcination of Yb₂O₃· x H₂O at 500°C had very small voids and the voids were enlarged to 35 Å in diameter by calcination at 800°C.     

A Novel Way to Synthesize Yttrium Aluminum Garnet from Metal–Inorganic Precursors

Yttrium aluminum garnet (YAG, Y₃Al₅O₁₂) was synthesized by sol–gel processing from the stoichiometric amounts of aluminum pellets, Y(NO₃)₃·6H₂O, and Al(NO₃)₃·9H₂O or AlCl₃·6H₂O, with suitable kinds of acid (citric acid, acetic acid, etc.) as catalysts. Polycrystalline YAG powder was obtained by drying the YAG precursor followed by calcination at temperatures above 900°C. Thermogravimetry/differential thermal analysis and Fourier transform infrared specotrscopic analyses in air showed an exothermic peak at ∼900°C, attributed to the formation of a polycrystalline YAG phase and weight loss of 60% at 1000°C, caused by the decomposition of hydroxyl and NO₃⁻, etc. X-ray diffraction analysis showed that YAG can be formed at 900°C, and no other intermediate was observed. In particular, the YAG sol can be used for dry-spinning fibers with the aid of some organic polymer.     

Calcium Phosphate Cements Prepared by Acid–Base Reaction

We investigated the characteristics of calcium phosphate cements (CPC) prepared by an exothermic acid–base reaction between NH₄H₂PO₄-based fertilizer (Poly-N) and calcium aluminate compounds (CAC), such as 3CaO · Al₂O₃ (C₃A), CaO · Al₂O₃ (CA), and CaO · 2Al₂O₃ (CA₂), in a series of integrated studies of reaction kinetics, interfacial reactions, in-situ phase transformations, and microstructure development. Two groups were compared: untreated and hydrothermally treated CPC specimens. The extent of reactivity of CAC with Poly-N at 25°C was in the following order: CA > C₃A ≫ CA₂. The formation of a NH₄CaPO₄· x H₂O salt during this reaction was responsible for the development of strength in the CPC specimens. The in-situ phase transformation of amorphous NH₄CaPO₄· x H₂O into crystalline Ca₅(PO₄)₃(OH) and the conversion of hydrous Al₂O₃ gel →γ-AIOOH occur in cement bodies during exposure in an autoclave to temperatures up to 300°C. This phase transformation significantly improved mechanical strength.     

Fabrication of Translucent Magnesium Aluminum Spinel Ceramics

A precursor for magnesium aluminum spinel powder, composed of crystalline ammonium dawsonite hydrate (NH₄Al(OH)₂CO₃·H₂O) and hydrotalcite (Mg₆Al₂(CO₃)(OH)₁₆·4H₂O) phases, was synthesized via precipitation, using ammonium bicarbonate as the precipitant. The precursor was characterized by differential thermal analysis/thermogravimetry, X-ray diffractometry, and scanning electron microscopy. Reactive spinel powder, which could be densified to translucency under vacuum at 1750°C in 2 h without additives, was obtained by calcining the precursor at 1100°C for 2 h.     

Low-Temperature Synthesis of Calcium Hexa-Aluminate

Calcium hexa-aluminate (CaO·6Al₂O₃) 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)₃·16H₂O for each mole of Ca(NO₃)₂·4H₂O. 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·Al₂O₃ and CaO·2Al₂O₃ were also formed as reaction intermediates in the reaction mix of CaO·6Al₂O₃. The kinetics of the formation of CaO·6Al₂O₃ 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·6Al₂O₃ was 40 kJ/mol.     

The System CaO-Al2O3-H2O

Phase equilibria have been determined in the system CaO-Al₂O₃-H₂O 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·Al₂O₃·6H₂O, and 4CaO·3Al₂O₃-3H₂O. 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·Al₂O₃ and 3CaO·Al₂O₃ 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.     

Synthesis of Titanate Derivatives Using Ion-Exchange Reaction

Two types of titanate derivatives, layered hydrous titanium dioxide (H₂Ti₄O₉· n H₂O) and potassium octatitanate (K₂Ti₈O₁₇) with a tunnellike structure, were synthesized using an ion-exchange reaction. Fibrous potassium tetratitanate (K₂Ti₄O₉· n H₂O) was prepared by calcination of a mixture of K₂CO₃ and TiO₂ with a molar ratio of 2.8 at 1050°C for 3 h, followed by boiling-water treatment of the calcined products for 10 h. The material then was transformed to layered H₂Ti₄O₉· n H₂O through an exchange of K⁺ ions with H⁺ ions using HCl. K₂Ti₈O₁₇ was formed by a thermal treatment of KHTi₄O₉· n H₂O. Pure KHTi₄O₉· n H₂O phase was effectively produced by a treatment of K₂Ti₄O₉ with 0.005 M HCl solution for 30 min. Thermal treatment at 250°–500°C for 3 h resulted in formation of only K₂Ti₈O₁₇.     

Synthesis and Characterization of MgAl2O4 Spinel Precursor from a Heterogeneous Alkoxide Solution Containing Fine MgO Powder

A precursor was synthesized from a heterogeneous alkoxide solution that contained fine MgO powder, which allowed the preparation of MgAl₂O₄ spinel powder with high sinterability characteristics. The precursor consisted of a mixture of boehmite (AlO(OH)) and a mixed hydroxide (Mg₄Al₂(OH)₁₄· 3H₂O). The spinel phase formed through two steps: (i) decomposition of the mixed hydroxide at low temperature and (ii) solid-state reaction between MgO and γ-Al₂O₃ at higher temperatures. Dense polycrystalline spinel could be obtained from the calcined powders at sintering temperatures as low as 1400°C.     

Preparation of Nanostructured Hexagonal Boron Nitride Powder

In this communication, we describe an inexpensive and feasible method for the preparation of hexagonal boron nitride (h–BN) nanorods in the absence of metal catalyst. Tertiary calcium phosphate (Ca₃(PO₄)₂) and ammonium biborate hydrate (NH₄HB₄O₇·3H₂O) were selected as starting materials where calcium phosphate was used as a diluting agent to prevent the formation of bulk B₂O₃ during the thermolysis of ammonium biborate hydrate. The mixture was nitrided at 900°C in the flowing ammonia and was transformed into h–BN nanorods after subsequent crystallization. After crystallization at 1650°C for 2 h, the unique microstructure of h–BN nanorods was observed.     

Compositional Model for Calcium Silicate Hydrate (C-S-H) Gels, Their Solubilities, and Free Energies of Formation

A compositional model based on available structural evidence is proposed for amorphous calcium silicate hydrogel. It is applicable to gels in the (Ca/Si),_solid range 1.0 to 1.4 and is formulated to take account of dimeric silicate species in the solid. Its composition is represented by Ca _x H_{6−2 x} Si₂O₇· z Ca(OH)₂· n H₂O where x and z are not independently obtainable; x + z , however, is evaluated from the Ca/Si ratio. The model is applied to representative solubility data; K_sp and free energies of formation for C-S-H's in this composition range are evaluated.     

Determination of Positions of Zeolitic Calcium Atoms and Water Molecules in Hydrothermally Formed Aluminum-Substiqtuted Tobermorite-1.1nm Using Synchrotron Radiation Powder Diffraction Data

The crystal structure of hydrothermally formed Al-substituted tobermorite-1.1nm (Ca_4.9Si_5.5Al_0.5O_16.3(OH)_0.7·5H₂O) has been analyzed using synchrotron radiation powder diffraction data. Crystallographic positions of a zeolitic Ca atom and three water molecules in the channel of the framework were determined by the Monte Carlo method and subsequent Rietveld refinement. The Ca atom splits into two sites at a distance of 0.161 nm apart, and it is coordinated with the three water molecules and the three oxygen atoms belonging to the framework. Al atoms preferably substitute a part of the Si atoms at the "bridging SiO₄" tetrahedra rather than at those of the "chain middle group SiO₄" tetrahedra.     

Chemical Preparation of the Binary Compounds in the Calcia-Alumina System by Self-Propagating Combustion Synthesis

The binary compounds Ca₃Al₂O₆ (C₃A), Ca₁₂Al₁₄O₃₃ (C₁₂A₇), CaAl₂O₄ (CA), CaAl₄O₇ (CA₂), and CaAl₁₂O₁₉ (CA₆) in the CaO-Al₂O₃ system have been synthesized as high-compound-purity ceramic powders by using the self-propagating combustion synthesis (SPCS) method. Materials characterization of the above-mentioned phases was performed via powder X-ray diffractometry (XRD), Fourier transform infrared spectroscopy, scanning electron microscopy, and energy-dispersive X-ray spectroscopy. The structural characterization of the C₁₂A₇ phase has been performed via Rietveld analysis on the powdered XRD samples. It has hereby been shown that, by using this synthesis procedure, it should be possible to manufacture high-purity ceramic powders of CA, CA₂, and C₁₂A₇ at 850°C, C₃A at 1050°C, and CA₆ at 1200°C in a dry-air atmosphere.     

The System MgO─P2O5─H2O at 25°C

The phase diagram for the ternary system MgO─P₂O₅─H₂O at 25°C has been constructed. The magnesium phosphates represented are Mg(H₂PO₄)₂· n H₂O ( n = 4, 2, 0), MgHPO₄·3H₂O, and Mg₃(PO₄)₂· m H₂O ( 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 P₂O₅ as their 10th roots has been employed. With the exception of MgHPO₄·3H₂O, the magnesium phosphates are incongruently soluble. Because incongruency is associated with a peritectic-like reaction, the phase Mg₂(PO₄)₃· 8H₂O persists metastably for an extended period.     

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.     

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.