NMR Studies of Fluorine in Aluminosilicate–Lanthanum Fluoride Glasses and Glass-Ceramics

NMR determinations of fluorine environments in transparent oxyfluoride glass-ceramics were made to learn about the crystallization of LaF₃, as well as to ascertain the structural role of fluorine in the surrounding glassy matrix. The fraction of fluorine in LaF₃ was measured as a function of heat treatments, demonstrating significant differences between glasses modified with barium and those containing sodium. The results of these measurements showed that not all of the fluorine formed LaF₃ in these glass-ceramics, with resolution of additional fluoride sites at −135 and −185 ppm, due primarily to Si–F and Al–F bonding, respectively. Not only is the evidence of Si–F bonding unexpected, given the presence of aluminum, but the amount of Si–F bonding is sensitive to the type of modifier in the glass. Samples containing barium oxide as the modifier showed a higher fraction of Si–F bonding than those modified with sodium oxide.     

Formation of a Highly Protective Amorphous Aluminum Silicate Layer on Steel during Granite–Dry Steam Interaction

Formation of an amorphous Al₂Si₂O₅ layer on a steel pipe surface, after granite–dry steam interaction in the presence of copper, has been determined by XRD analysis and SEM (with energy dispersive X-ray microanalysis). Kinetic data indicate high-protective properties of the Al₂Si₂O₅ layer, which formed a three-dimension substrate ∼5 μm thick, after 100 h exposure.     

Structure of Sodium Aluminosilicate Glasses

A series of sodium aluminosilicate glasses composed of varying ratios ( R ) of Al₂O₃/Na₂O (0.25 R 2.0) has been simulated with the molecular dynamics technique using a tetrahedral form of a three-body interaction potential. Extrema in the activation energies for sodium diffusion and in the diffusion constants for all of the atomic species were observed for glasses with equal concentrations of Al₂O₃ and Na₂O ( R = 1.0). These changes corresponded to the minimum observed experimentally in the activation energy for electrical conductivity and to the maximum observed in the viscosity for glasses with compositions of R = 1.0. The coordination of aluminum remained 4 over the entire compositional range, negating the need to invoke a coordination change of aluminum to explain the changes in the physical properties. The changes to the simulated physical properties as R passed through the equivalence point were attributed to the elimination of nonbridging oxygen, to the introduction of oxygen triclusters, and to changes in the distribution of ring structures within the glass networks.     

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.     

Phase Diagram of the System KF–AlF3

The system KF–AlF₃ was reinvestigated precisely by differential thermal analysis, X-ray diffractometry, and visual observation. All of the samples for the present investigation were prepared by solution synthesis. The results verified the existence of 2KF·AlF₃ (K₂AlF₅) and KF·4AlF₃ in the phase diagram; both compounds were orthorhombic. The cell parameters of the compounds were, respectively, a = 10.87 ± 0.03 Å, b = 10.36 ± 0.01 Å, c = 7.83 ± 0.03 Å, and a = 7.89 ± 0.01 Å, b = 7.57 ± 0.01 Å, c = 6.94 ± 0.01 Å. KAlF₄ was confirmed to melt congruently at 575°± 2°C by careful examination.     

Incorporation of Al and Na in Hydrothermally Synthesized Tobermorite

Calcium silicate hydrate and its Al‐substituted form synthesized by a hydrothermal process were investigated by X‐ray diffraction, compositional analysis, and magic‐angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy, in order to determine the mechanism of Al and Na incorporation in the tobermorite structure with varying molar ratios of Ca/Si and Al/Si. At a high molar ratio of Ca/Si, the silicate chains of tobermorite are ruptured, the degree of polymerization of the silicate chains is lowered, and the high calcium concentration lowers the content of Na₂O in the structure. Solid‐state ²⁹Si and ²⁷Al MAS NMR spectroscopy confirm that all Al atoms were incorporated in the silicate chains of tobermorite. The tetrahedrally coordinated Al (Al(IV)) could either act as the bridging tetrahedron () for the dreierketten chain of tobermorite, or be present in Q³ sites that link two dreierketten chains together. Therefore, the degree of polymerization of the silicate chains of tobermorite is increased at high molar ratio of Al/Si. Furthermore, the greater charge deficit due to the replacement of Si⁴⁺ by Al³⁺ ions is compensated by increased adsorption or binding of Na⁺.     

Pressureless Sintering and Mechanical and Biological Properties of Fluor-hydroxyapatite Composites with Zirconia

Fluor-hydroxyapatite (FHA) fabricated by a reaction between fluorapatite (FA) and hydroxyapatite (HA) was mixed with ZrO₂ to produce FHA–ZrO₂ composites. When the relative amount of FA to HA increased, the decomposition of the composite was decreased gradually because of the formation of thermally stable FHA solid solutions. With such suppression of decomposition, the FHA–ZrO₂ composites retained fully densified bodies. As a result, significant enhancements in mechanical properties, such as hardness, flexural strength, and fracture toughness, were achieved as the relative amount of FA to HA increased. The highest values in strength and toughness were 220 MPa and 2.5 MPa·m^1/2, respectively, with FHA–40 vol% ZrO₂ composites. In vitro proliferation of osteoblast-like cells (MG63) on the composites showed behavior similar to that observed on pure HA and FHA. Alkaline phosphatase (ALP) activity of the growing cells (HOS) on the composites was slightly down-regulated compared with that on pure HA and FHA at prolonged periods.     

The Distortion‐Adjusted Change of Thermal Expansion Behavior of Cubic Magnetic Semiconductor (Sc1−xMx)F3 (M = Al,Fe)

For the study of negative thermal expansion (NTE) compounds, it is critical to effectively control the thermal expansion. In this letter, a chemical approach has been taken to control the thermal expansion behavior in ScF₃ which has a strong NTE. Owing to the difference of radius of substituting ions, local distortion inevitably emerges in the lattice matrix, which is verified by pair distribution function analysis of high‐resolution synchrotron X‐ray scattering. It is a valuable clue that the thermal expansion behaviors in the ScF₃ based systems and other trifluorides are correlated closely to structural distortion of metal‐F‐metal linkages. In addition, the introduction of 3d transition‐metal enables its semiconductor and ferromagnetic characteristics. This study provides important reference opinion for the control of thermal expansion and introduction of multifunctionalization for those NTE compounds with open framework structure.     

Zero thermal expansion in cubic MgZrF6

Isotropic zero thermal expansion (ZTE) is rare but intriguing physical property in materials. Here, we report an isotropic ZTE property in a double ReO₃‐type compound of MgZrF₆, which exhibits a negligible value of coefficient of thermal expansion (α_l = ?7.94 × 10^?7 K^?1 (XRD), α_l = ?4.22 × 10^?7 K^?1 (dilatometry), 300‐675 K). The ZTE mechanism of MgZrF₆ is understood by the joint studies of temperature dependence of crystal structure and lattice dynamics. Interestingly, different magnitudes of atomic displacement parameters (ADPs) for the fluorine atoms in MZrF₆ (M = Ca, Ni, Mg) are found. The strong temperature sensitivity of ADPs demonstrates intensive transverse thermal vibration of fluorine atoms, which contributes essentially to the negative thermal expansion of CaZrF₆. By contrast, for NiZrF₆ with positive thermal expansion, the temperature response of ADPs is weak. Moderate transverse thermal vibration takes place in MgZrF₆, and ZTE appears. Furthermore, lattice dynamics of MgZrF₆ is studied by temperature‐dependent Raman spectroscopy, which reveals the ZTE mechanism. In particular, the F_2g and A_g modes, corresponding to the bending and stretching vibrations of fluorine atoms, respectively, neither soften nor harden over the whole temperature range, which is correlated with the isotropic ZTE property of MgZrF₆.     

Optical properties of novel oxyfluoride glasses on the systems of LaF3–LaO3/2–NbO5/2 and LaF3–LaO3/2–NbO5/2–AlO3/2

Oxyfluoride glasses of xLaF₃–(60 − x)LaO_3/2–40NbO_5/2 (x = 0, 5, 10, 35) and xLaF₃–(60 − x)LaO_3/2–30NbO_5/2–10AlO_3/2 (x = 0, 10, 20, 30) were prepared using a levitation technique. Both the glass-transition temperature, T_g, and onset crystallization temperature, T_c, were lowered by substituting a part of the oxygen with fluorine in the glasses. An appropriate amount of fluorine maximized the difference between the temperatures, ΔT (= T_c − T_g), indicating the improvement in the glass-forming ability. The atomic packing densities of the glasses were approximately 60%, which gradually increased with the fluorine content. The absorption edge of the glasses shifted toward the shorter wavelength region in the ultraviolet spectra and toward the longer region in the infrared spectra by fluorine substitution. In addition, in one of the oxyfluoride glasses, a wide transparency from 307 nm to 9.2 µm was realized. Furthermore, the glass exhibited superior optical properties, with a combination of a high refractive index, n_d, of 2.020 and low wavelength dispersion, v_d, of 30.1. The effect of fluorine substitution on the n_d and its v_d was analyzed using the Lorentz–Lorenz dispersion formula.     

Fluorine as a Donor Dopant in Barium Titanate Ceramics

We have studied the electrical properties and microstructure of fluorine-doped BaTiO₃ ceramics. The samples were prepared using a classical ceramic technology that involved the calcination of intimately mixed powders of BaCO₃, TiO₂, and BaF₂. When the samples were sintered in untreated ambient air, the fluorine from the sample reacted with water vapor and formed gaseous HF. To prevent this hydrolysis of the fluorine, we sintered the samples in dried air. The fluorine-doped BaTiO₃ ceramics sintered in a dry atmosphere showed microstructures and electrical properties typical of donor-doped BaTiO₃. The samples containing up to 0.3 mol% of fluorine were coarse-grained, semiconducting, and displayed a remarkable PTCR effect. In contrast, the samples with a higher fluorine concentration were fine grained and insulating. A SIMS elemental mapping of the samples showed that the fluorine was distributed throughout the microstructure of the semiconducting samples; however, the fluorine concentration was enriched at grain boundaries and in the BaTi₂O₅ intergranular phase.     

Fiber Strength Retention of Lanthanum- and Cerium Monazite-Coated Nextel™ 720

Nextel™ 720 fibers were coated with LaPO₄ and CePO₄ monazite. The coatings were applied using washed and unwashed rhabdophane sols derived from La(NO₃)₃/(NH₄)₂HPO₄ and a washed sol derived from Ce(NO₃)₃/H₃PO₄. The coatings were cured in-line at 900°–1300°C. Multiple coatings were also applied. Fiber strength was retained after coating with washed sols, but not with unwashed sols. These results are consistent with earlier work on LaPO₄ monazite fiber coatings derived from La(NO₃)₃/H₃PO₄.