Mesoporous AlPO4 Glass from a Simple Aqueous Sol–Gel Route

Transparent and colorless AlPO₄ gel and glass are prepared via a simple aqueous sol–gel route using aluminum lactate and phosphoric acid as precursors. The stoichiometric AlPO₄ glass derived from this sol–gel route has a mesoporous structure with a surface area of 504 m²/g after calcination to 600°C. With increasing gel-to-glass processing temperature, the average degree of P/Al connectivity increases. After sample calcination at 600°C for 4 h, ²⁷Al MAS NMR spectra indicate that aluminum is almost completely converted into AlO₄ units. ²⁷Al{³¹P} rotational echo double resonance and ³¹P{²⁷Al} rotational echo adiabatic passage double resonance NMR experiments as well as ²⁷Al and ³¹P MAS NMR results further confirm that the prepared AlPO₄ glass has a three-dimensional network based on alternating Al(OP)₄ and P(OAl)₄ tetrahedral units in analogy to the local structure of crystalline AlPO₄.     

Hydration Kinetics and Phase Stability of Dicalcium Silicate Synthesized by the Pechini Process

Reactive dicalcium silicate (Ca₂SiO₄) has been synthesized by the Pechini process, and hydration kinetics studied. With increasing calcination temperature, the amorphous product first crystallizes to α'_L-phase and subsequently to the ß- and γ-phases. The specific surface area, ranging from 40 to 1 m²/g, strongly depends on the calcination temperature of 700°-1200°C for 1 h. Samples with a high surface area have a high water demand; a water/cement ratio >2.0 is required to produce formable pastes in some instances. Hydration kinetics are determined by XRD, ²⁹Si magic-angle spinning nuclear magnetic resonance (MAS NMR), and differential scanning calorimetry/thermogravimetry (DSG/TG). The hydration rate depends only on the surface area, not on the polymorph. Complete hydration occurs in as early as 7 d. Very little calcium hydroxide (Ca(OH)₂) is formed in the most reactive specimens (calcined at 700° and 800°C), which indicates the Ca/Si ratio in C-S-H gels is ∼2.0, but more Ca(OH)₂ forms from samples calcined at higher temperature. The silicate structure of the hydrated Ca₂SiO₄ pastes is investigated using ²⁹Si MAS NMR spectroscopy and trimethylsilylation analysis.     

Local Structure of xAl2O3· (1 −x)NaPO3 Glasses: An NMR and XPS Study

A series of x Al₂O₃· (1 − x )NaPO₃ glasses (0 ≤ x ≤ 0.275) were prepared and characterized by magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy and by X-ray photoelectron spectroscopy (XPS). ²⁷AI MAS NMR spectra reveal that: at low alumina contents ( x < 0.125), Al is in dominantly octahedrally coordinated Al(OP)₆ structural environments; in glasses with x > 0.125, Al(OP)₄ environments are increasingly favored; and at x = 0.275, most Al is tetrahedrally coordinated. 5-coordinated Al environments also appear to be present. Variations in the ³¹P MAS NMR spectra are consistent with bonding between neighboring P and Al polyhedra. Quantitative changes in the oxygen bonding, determined from the O 1 s spectra obtained by XPS, also reflect these structural changes. The effects of alumina content on the relative concentration of nonbridging oxygen (PO⁻) are quantitatively described by a simple structural model derived from the MAS NMR data. The thermal expansion coefficients and glass transition temperatures are shown to be sensitive to these structural changes.     

Hydration in the System Ca2SiO4–Ca3(PO4)2 at 90°C

Compositions along the Ca₂SiO₄–Ca₃(PO₄)₂ join were hydrated at 90°C. Mixtures containing 15, 38, 50, 80, and 100 mol% Ca₃(PO₄)₂ were fired at 1500°C, forming nagelschmidtite + a ¹-CaSiO₄, A -phase and silicocarnotite and a -Ca₃(PO₄)₂, respectively. Hydration of these produces hydroxylapatite regardless of composition. Calcium silicate hydrate gel is produced when Ca₂SiO₄≠ 0 and portlandite when Ca₂SiO₄ is >50%. Relative hydration reactivities are a -Ca₃(PO₄)₂ > nagelschmidtite > α ¹-Ca₂SiO₄ > A -phase > silicocarnotite. Hydration in the presence of silica or lime influences the amount of portlandite produced. Hydration in NaOH solution produces 14-A tobermorite rather than calcium silicate hydrate gel.     

Highly Reactive β-Dicalcium Silicate: I, Hydration Behavior at Room Temperature

The hydration behavior at 25°C of β-dicalcium silicate synthesized from hillebrandite (Ca₂,(SiO₃)(OH)₂) at 600°C was studied over a period of 224 d. The hydration rate of the β-dicalcium silicate having fibrous crystals with specific surface area of 7 m²/g is extremely rapid. For water/solids ratios of 0.5 and 1.0, the hydration reaction is completed in 28 and 14 d, respectively. The hydrate contains almost no Ca(OH)₂, and its Ca/Si ratio is close to 2. SEM observations indicate that the hydrate forms an outer shell on the surface of β-dicalcium silicate and grows inwards. The silicate anion structure is considered to consist of dimers and single-chain structures from ²⁹Si MAS NMR. Variations of physical properties of press-formed bodies have also been discussed.     

Synthesis and Hydration Characteristics of Alinite Cement

A chlorine-bearing alinite cement was synthesized using reagent-grade chemicals, and the phase evolution and hydration behavior of the alinite clinker were examined. The effects of the MgO content on alinite formation and hydration also were investigated. Alinite began to appear at 1000°C from β-C₂S, C₁₁A₇CaCl₂, and unreacted raw materials, and an almost single-phase alinite was obtained at 1300°C. The alinite phase also was produced without MgO addition. However, CaO, β-C₂S, and C₁₁A₇CaCl₂ phases were present. Alinite cements hydrated rapidly after a short incubation period, and the hydration products were C-S-H gels, Ca(OH)₂, and a Fridel's saltlike phase. The local environmental changes of silicon and aluminum during the formation and hydration of alinite were determined using magic-angle-spinning nuclear magnetic resonance spectroscopy. The Cl⁻-ion exsolution from the alinite paste during hydration was measured using ion chromatography.     

Highly Reactive β-Dicalcium Silicate: II, Hydration Behavior at 25°C Followed by 29Si Nuclear Magnetic Resonance

The hydration behavior at 25°C of highly reactive β-dicalcium silicate synthesized from hillebrandite (Ca₂(SiO₃)(OH)₂) was studied over a period of 7 to 224 d using ²⁹Si magic-angle spinning nuclear magnetic resonance (MAS NMR). The hydration product, C-S-H, contains Q² and Q¹ silicate tetrahedra, the chemical shifts of which are independent of the water/solid (w/s) ratio and curing time. Until the reaction is completed, the amounts of Q¹ and Q² formed are independent of the w/s ratio, being determined only by the degree of reaction. The ratio Q²/Q¹ increases as the reaction progresses and as the curing time becomes longer. From the values of Q²/Q¹, it appears that the hydrate is a mixture of dimers and short single-chain polymers. The Ca/Si ratio of the hydrate is high, taking values close to 2.0, but the Ca/Si ratio does not influence the Q²/Q¹ ratio. It was also found that the NMR peak intensities allow quantitative assessment similar to XRD.     

Synthesis of AlN Nanopowder from γ-Al2O3 by Reduction–Nitridation in a Mixture of NH3–C3H8

Aluminum nitride (AlN) powders were synthesized by gas reduction–nitridation of γ-Al₂O₃ using NH₃ and C₃H₈ as the reactant gases. AlN was identified in the products synthesized at 1100°–1400°C for 120 min in the NH₃–C₃H₈ gas flow confirming that AlN can be formed by the gas reduction–nitridation of γ-Al₂O₃. The products synthesized at 1100°C for 120 min contained unreacted γ-Al₂O₃. The ²⁷A1 MAS NMR spectra show that Al–N bonding in the product increases with increasing reaction temperature, the tetrahedral AlO₄ resonance decreasing prior to the disappearance of the octahedral AlO₆ resonance. This suggests that the tetrahedral AlO₄ sites of the γ-Al₂O₃ are preferentially nitrided than the AlO₆ sites. AlN nanoparticles were directly formed from γ-Al₂O₃ at low temperature because of this preferred nitridation of AlO₄ sites in the reactant. AlN nanoparticles are formed by gas reduction–nitridation of γ-Al₂O₃ not only because the reaction temperature is sufficiently low to restrict grain growth, but also because γ-Al₂O₃ contains both AlO₄ and AlO₆ sites, by contrast with α-Al₂O₃ which contains only AlO₆.     

Application of Selective 29Si Isotopic Enrichment to Studies of the Structure of Calcium Silicate Hydrate (C-S-H) Gels

Selective isotopic enrichment of SiO₂ with ²⁹Si in a mixture with tricalcium silicate (C₃S) has allowed the Si from this phase to be effectively labeled during the course of the hydration reaction, thus isolating its contribution to the reaction. A double Q₂ signal has been observed in ²⁹SI solid-state MAS NMR spectroscopy of C-S-H gels of relatively low Ca/Si ratio, prepared by hydration or by carbonation of a C₃S paste. The origin of the weaker, downfield peak is discussed and tentatively attributed to bridging tetrahedra of a dreierkette silicate chain structure.     

Character of Hydration of 3CaO.Al2O3

The C₃A compacts were hydrated and the reaction was studied by DTA, X-ray diffraction, mercury porosimetry, and volume change analysis. The hexagonal hydroaluminates C₂AH₈ and C₄AH₁₉ formed at 2°, 12°, and 23°C by a direct mechanism between C₃A and H₂O. The hydration reaction at 52° and 80°C was stopped by formation of C₃AH₆ around the C₃A grains. The rate of conversion of the hexagonal hydrates to cubic C₃AH₆ increased with temperature. Volume change analysis confirmed that C₃AH₆ grows epitaxially on the surface of the C₃A grain. The reaction at this surface and the passage of water through the layer of hexagonal hydroaluminates control the overall reaction rate. The conversion of the hexagonal hydrates to C₃AH₆ accelerates the reaction by removing the layer of products from around the C₃A grain by a solution mechanism. At 52° and 80°C, C₃AH₆ may form without the intermediate formation of the hexagonal hydrate.     

Disorder and Dynamics in Pollucite from 133Cs and 27Al NMR

Pollucite, CsAlSi₂O₆, a Cs polymorph of leucite (KAlSi₂O₆), has been proposed for ceramic immobilization of ¹³⁵Cs and ¹³⁷Cs fission products. ¹³³Cs NMR of both low- (tetragonal) and high-temperature (cubic) forms of pollucite exhibit a considerable distribution of local Cs environments. ²⁹Si and ²⁷Al NMR data from directly prepared pollucite show greater Al/Si disorder than either leucite, or pollucite produced by ion exchange. Little evidence for Cs motion is observed in tetragonal or cubic pollucite, and only at high temperatures (∼850°C) is any substantial dynamic behavior detected. Dynamic NMR lineshape calculations allow a determination of the frequency of Cs motion and diffusivity.     

Physicochemical Mechanism for the Continuous Reaction of γ-Al2O3-Modified Aluminum Powder with Water

Previous experiments showed that γ-Al₂O₃-modified Al powder could continuously react with water and generate hydrogen at room temperature under atmospheric pressure. In this work, a possible physicochemical mechanism is proposed. It reveals that a passive oxide film on Al particle surfaces is hydrated in water. OH⁻ ions are the main mobile species in the hydrated oxide film. When the hydrated front meets the metal Al surface, OH⁻ ions react with Al and release H₂. Because of the limited H-soluble capacity in small Al particles and the low permeability of the hydrated oxide film toward H⁺ species, H₂ molecules accumulate and form small H₂ gas bubbles at the Al:Al₂O₃ interface. When the reaction equilibrium pressure in H₂ bubbles exceeds a critical gas pressure that the hydrated oxide film can sustain, the film on the Al particle surfaces breaks and the reaction of Al with water continues. As the surface oxide layer on modified Al particles has a lower tensile strength, the critical gas pressure in H₂ bubbles is lower so that under an ambient condition, the reaction of modified Al particles with water is continuous. The proposed mechanism was further confirmed by a new experiment showing that the as-received Al powder could continuously react with water at temperatures above 40°C and under low vacuum, because the vacuum makes the critical gas pressure in H₂ bubbles decrease as well.     

α-Dicalcium Silicate Hydrate: Preparation, Decomposed Phase, and Its Hydration

α-C₂SH can be synthesized by hydrothermal treatment of lime and silicic acid for 2 h at 200°C. When heated to 390–490°C, α-C₂SH dissociates through a two-step process to form an intermediate phase plus some γ-C₂S. This appears to be a new dicalcium silicate different from known dicalcium silicates—α, α'_L, α'_H, β, and γ phase—and is stable until around 900°C. At 920–960°C, all the phases are transformed to the α'_L phase. The intermediate phase has high crystallinity and is stable at room temperature. ²⁹ Si MAS NMR measurements indicate the possibility that it contains both protonated and unprotonated monosilicate anions. The intermediate phase that has passed through the α'phase at higher temperature yields β-C₂S on cooling. The intermediate phase is highly active, and completed its hydration in 1 day ( w/s = 1.0, 25°C). Among the crystalline calcium silicate hydrates with Ca/Si = 2.0, it is hillebrandite that yields β-C₂S at the lowest temperature.     

In Situ Reaction Synthesis, Electrical and Thermal, and Mechanical Properties of Nb4AlC3

In this work, a bulk Nb₄AlC₃ ceramic was prepared by an in situ reaction/hot pressing method using Nb, Al, and C as the starting materials. The reaction path, microstructure, physical, and mechanical properties of Nb₄AlC₃ were systematically investigated. The thermal expansion coefficient was determined as 7.2 × 10⁻⁶ K⁻¹ in the temperature range of 200°–1100°C. The thermal conductivity of Nb₄AlC₃ increased from 13.5 W·(m·K)⁻¹ at room temperature to 21.2 W·(m·K)⁻¹ at 1227°C, and the electrical conductivity decreased from 3.35 × 10⁶ to 1.13 × 10⁶Ω⁻¹·m⁻¹ in a temperature range of 5–300 K. Nb₄AlC₃ possessed a low hardness of 2.6 GPa, high flexural strength of 346 MPa, and high fracture toughness of 7.1 MPa·m^1/2. Most significantly, Nb₄AlC₃ could retain high modulus and strength up to very high temperatures. The Young's modulus at 1580°C was 241 GPa (79% of that at room temperature), and the flexural strength could retain the ambient strength value without any degradation up to the maximum measured temperature of 1400°C.     

Hydration of Tricalcium Silicate Followed by 29Si NMR with Cross-Polarization

The use of cross-polarization (CP) NMR in conjunction with magic angle sample spinning (MASS) to examine the hydration reaction of tricalcium silicate (C₃S) is described. In particular the very early stages of the reaction both with and without admixtures has been studied as well as the hydration in a ball mill. The combination of CP and non-CP ²⁹Si NMR permits the distinction between silicate units associated with protons, i.e., in hydrated material, and those in anhydrous material. It has been found that in paste hydration there is steady formation of a small amount of hydrated monomeric silicate units during the induction period. In ball mill hydration the formation of the crystalline calcium silicate hydrate, afwillite, which contains only hydrated monomeric silicate species, can be monitored. These results are interpreted in terms of possible mechanisms for C₃S hydration.     

Polymerized Complex Route to Synthesis of Pure Y2Ti2O7 at 750°C Using Yttrium-Titanium Mixed-Metal Citric Acid Complex

A polymerized complex technique was used to prepare high-purity pyrochlore Y₂Ti₂O₇ powders at 750°C. Heating of a mixed solution of citric acid (CA), ethylene glycol (EG), and yttrium and titanium ions, with a molar ratio of CA:EG:Y:Ti = 5:20:1:1, at 130°C produced a yellowish transparent polymeric gel without any precipitation; this material was used subsequently as a precursor for Y₂Ti₂O₇. Based on the results of ¹³C-NMR spectroscopy, it was suggested that a mixed-metal (Y,Ti)-CA₃ chelate complex formed in a starting CA/EG solution. The formation of pure pyrochlore Y₂Ti₂O₇ occurred when the precursor was heat-treated in a furnace set at 750°C in static air for 4 h.     

Low-Temperature Formation of Aluminum Orthophosphate

Factors influencing the low-temperature formation of AIPO₄ and its precursor phases, AIPO₄· x H₂O (1 x 2), were investigated. AIPO₄ formed by reaction between 33.3 wt% H₃PO₄ solution and alumina. Five aluminas (three anhydrous and two hydrated) were utilized. Each differed in particle size, surface area, and crystallinity. The reaction temperatures investigated were 113°, 123°, and 133°C. The high-surface-area aluminas were sufficiently reactive in the phosphoric acid solution at these temperatures to produce crystalline reaction products. However, only hydrated forms of AIPO₄, AIPO₄· x H₂O (1 x 2), crystallized directly out of solution. x generally decreased as the curing temperature was increased. Upon dehydration of these hydrated reaction products, anhydrous AIPO₄ was formed, primarily in the berlinite and/or cristobalite modifications. Both the temperature of reaction and the alumina used influence the hydrates that form. In turn, the hydrates which form, the macroscopic assemblages into which they may crystallize, and the morphologies of the crystallites all affect the polymorphic form and the crystallinity of the anhydrous AIPO₄ phase ultimately produced on dehydration. Phase-pure and highly crystalline AIPO₄-cristobalite (the high-temperature modification) was formed by the dehydration of AIPO₄·H₂O at a temperature as low as 113°C.     

Direct Synthesis and Hydration of Calcium Aluminosulfate (Ca4Al6O16S)

Calcium aluminosulfate (Ca₄Al₆O₁₆S or C₄A₃̄) was prepared by direct synthesis from calcium and aluminum nitrates, and aluminum sulfate. CaAl₄O₇(CA₂) formed as an intermediate at 900°C, and C₄A₃̄ was the main phase after calcination at 1100°C. The specific surface areas after calcination at 1100° and 1300°C were ∼2.5 and 1 m²/g, respectively. Hydration was investigated using XRD, DSC, SEM, conduction calorimetry, and solid-state ²⁷Al MAS-NMR spectroscopy. Calorimetry showed that the induction period was longer than that of a sample prepared using conventional solid-state sintering, and this was attributed to the formation of amorphous coatings. Crystalline hydration products, principally calcium monoaluminosulfate hydrate and aluminum hydroxide, appeared subsequently. Although the induction period was very long, complete hydration occurred as early as 3 d in the sample calcined at 1100°C and was 91% complete in the sample calcined at 1300°C.     

Kinetics of Hydration of Monocaldum Aluminate

Hydration of CaAl₂O₄ (CA) was studied by calorimetry, analysis of the liquid phase, measurement of the combined water, and electron microscopy. During the induction period, the solution remains almost unchanged and is equilibrated temporarily with both superficially intrusion-hydrated CA particles and Al(OH)₃ gel formed by dissociation of Al(OH)₄^– ions, the solubility of the Al(OH)₃ gel being 10^–4.24 molkg^–1 at 25°C, while the intrusion-hydrated layer on the CA particles grows following a nearly linear law to reach a critical thickness (∼3 nm at 10° to 20°C, or 12 nm at 30°C). At this point destruction of the layer occurs, nuclei of hydrous compounds are generated, and the induction period terminates. Subsequent reaction proceeds in accordance with the rate equation of Schiller based on the dissolution-crystallization mechanism.     

Formation Kinetics of Calcium Aluminates

The kinetics of formation of calcium aluminates was studied by firing the reaction mixes in the temperature range 12000° to 1460°C for reaction times from 15 to 360 min. Phases formed were determined by taking X-ray diffractograms of the samples. It was observed that all stable calcium aluminates were formed and that monocalcium aluminate (CA) grew with calcium dialuminate (CA₂) in a 1:2 reaction mix of CaO and Al₂O₃. CA reacted further with Al₂O₃ to form CA₂. The formation of CA₂ obeyed the rate law equation 1 - (1 - x )^1/3= Kt / r ². The activation energy for the system (140 kJ·mol⁻¹ (33.4 kcal · mol⁻¹)) was determined by the Arrhenius equation.