17O NMR Spectroscopy of α-TeO2 and Na2TeO3

The synthesis of ¹⁷O-enriched α-tellurite (α-TeO₂) is described. TeO₂ is obtained stochiometrically by the reaction of tellurium isopropoxide with ¹⁷O-enriched H₂O. The reaction is mild and simple and opens the field of tellurite-based ceramics to ¹⁷O nuclear magnetic resonance spectroscopy. We also report the first ¹⁷O nuclear magnetic resonance spectra of α-TeO₂ and Na₂TeO₃. Their isotropic chemical shifts, δ_iso, are 180 ppm and 158 ppm, respectively, and their quadrupolar coupling parameters are C_Q=7.48 MHz and η=0.43 for α-TeO₂, and C_Q=6.63 MHz and η=0.33. By using extended Hückel tight binding calculations, we interpret the chemical shifts of tetravalent inorganic oxide network formers (SiO₂, GeO₂, and TeO₂) in terms of the local paramagnetic shielding effect. We also show that this is the predominant effect in determining the chemical shifts of non-bridging oxide sites in this type of network.     

Homogeneous ZrO2–Al2O3 Composite Prepared by Nano-ZrO2 Particle Multilayer-Coated Al2O3 Particles

ZrO₂–Al₂O₃ nanocomposite particles were synthesized by coating nano-ZrO₂ particles on the surface of Al₂O₃ particles via the layer-by-layer (LBL) method. Polyacrylic acid (PAA) adsorption successfully modified the Al₂O₃ surface charge. Multilayer coating was successfully implemented, which was characterized by ξ potential, particle size. X-ray diffraction patterns showed that the content of ZrO₂ in the final powders could be well controlled by the LBL method. The powders coated with three layers of nano-ZrO₂ particles, which contained about 12 wt% ZrO₂, were compacted by dry press and cold isostatically pressed methods. After sintering the compact at 1450°C for 2 h under atmosphere, a sintered body with a low pore microstructure was obtained. Scanning electron microscopy micrographs of the sintered body indicated that ZrO₂ was well dispersed in the Al₂O₃ matrix.     

Processing and Properties of Eu3+:LiTaO3 TransparentGlass–Ceramic Nanocomposites

We report here the processing and properties of transparent glass and glass–ceramic nanocomposites in the Li₂O–Ta₂O₅–SiO₂–Al₂O₃ system in the presence of Eu₂O₃ as luminescent probe. The formation of the LiTaO₃ crystal phase, the crystallite size, and the morphology with the progression of heat treatment have been examined by X-ray diffraction (XRD), transmission electron microscopy (TEM), and Fourier transformed infrared reflectance spectroscopy measurements. The crystallite sizes obtained from XRD and TEM are found to increase with heat-treatment time and vary in the range of 2–20 nm. The measured photoluminescence spectra exhibit emission transitions of ⁵D_0,1→⁷F _j ( j =0, 1, 2, 3, and 4) of Eu³⁺ ions. From the nature of the emission transitions, the site symmetry in the vicinity of Eu³⁺ ions has been found to be near C_3v in the glass–ceramic nanocomposites. An inverse correlation has been observed between the asymmetric ratio ( I _ED/ I _MD) of Eu³⁺ ions and the dielectric constant (ɛ_r), with an increase in the heat-treatment time of glass, which is caused by the dipole–dipole interaction.     

A New Low-Loss Microwave Dielectric Ceramic Sr4LaTiNb3O15

A high dielectric constant and low-loss ceramic with composition Sr₄LaTiNb₃O₁₅ has been prepared by the conventional solid-state ceramic route. This compound adopts an A₅B₄O₁₅ cation-deficient hexagonal perovskite structure and crystallizes in the trigonal system with unit cell parameters a =5.6307(2), c =11.3692(3) Å, V =312.16(2) ų, and Z =1. The dielectric properties of dense ceramics sintered in air at 1460°C have been characterized at microwave frequencies. The results show that the material affords a relatively high dielectric constant ɛ_r∼43, a high quality factor Q × f ∼44 718 GHz, and a low temperature coefficient of resonant frequency TC_f∼13 ppm/°C.     

A/B Site Modified CaTiO3 Dielectric Ceramics for Microwave Application

(Li_1/2Nd_1/2)²⁺ substitution into the A site and (Mg_1/3Ta_2/3)⁴⁺ substitution into the B site of CaTiO₃ ceramic were investigated, respectively. The modified CaTiO₃ dielectric ceramics prepared by conventional solid-state method exhibit single perovskite structure and improved dielectric properties. Optimal microwave dielectric properties of ɛ_r=112.6, Q × f =4480 GHz, τ_f=8.2 ppm/°C in [Ca_0.4(Li_1/2Nd_1/2)_0.6] TiO₃ and ɛ_r=60.2, Q × f =36900 GHz, τ_f=−10.1 ppm/°C in Ca[Ti_0.4(Mg_1/3Ta_2/3)_0.6] O₃ are obtained, which indicates their potential for microwave application. The effects of change of crystal structure on dielectric properties are also discussed.     

Dispersion of Alumina and Silicon Carbide Powders in Alumina Sol

Dispersion of Al₂O₃ and SiC particles in an alumina sol has been investigated through determination of particle-size distribution, zeta potential, and agglomerate morphology. The particle size of Al₂O₃ and SiC (as determined by the particle-size analyzer) is strongly affected by the presence of alumina sol in the solution. The average agglomerate size is decreased by at least 50%. The zeta potential of Al₂O₃ in 1 M alumina sol increases slightly, whereas that of SiC reverses its sign over a wide range of pH values. It is proposed that these effects are caused by AlO₄Al₁₂(OH)₂₄(H₂O)⁷⁺₁₂ sol clusters (1-2 nm in size) that are absorbed on the surface of the large (1-5 µm) ceramic particles. The electrostatic and steric effects of the cluster absorption help to control the dispersion and stabilize the suspension of ceramic particles in the alumina sol during wet processing. It is expected that the alumina-sol clusters can be used as an efficient, clean dispersant for single-phase and composite ceramic powders.     

Characterization of Synthetic and Naturally Occurring Clays by 27Al and 29Si Magic-Angle Spinning NMR Spectroscopy

Magic-angle spinning nuclear magnetic resonance (MASNMR) spectroscopy (²⁷Al) detected the coordination of Al in clays containing as little as 0.26% Al₂O₃. The ²⁹Si MASNMR of fluorphlogopite showed three distinct Si chemical environments which suggested short-range ordering. Synthetic laponite and mica-montmorillonite showed broad ²⁹Si resonances indicative of short-range disorder. A saponite showed four ²⁹Si resonances. Considerable insight into the short-range ordering of clays can be gained by ²⁷Al and ²⁹Si MASNMR.     

Solid-state NMR Evidence of 4-, 5, and 6-Fold Aluminum Sites in Roller-Quenched SiO2-A12O3 Glasses

The structures of roller-quenched SiO₂-Al₂O₃ glasses containing 10 to 50 wt% Al₂O₃ were investigated by TEM and high-resolution ²⁷Al and ²⁹Si magic angle sample spinning nuclear magnetic resonance (MASS-NMR) spectroscopy. The chemical shifts observed in the NMR spectra of these phase-separated (on the TEM scale) glasses provide evidence, for the existence of all three (4-, 5-, and 6-jold) Al-coordination units in these glasses and for the presence of A1 in both the Si-rich and Si-poor phases.     

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.     

Natural Abundance 43Ca NMR Spectroscopy of Tobermorite and Jennite: Model Compounds for C–S–H

There are few effective methods for characterizing the molecular scale structural environments of Ca²⁺ in hydrated cements, which has limited our ability to understand the structure of, for example, Ca–silicate hydrate (C–S–H). ⁴³Ca nuclear magnetic resonance (NMR) spectroscopy has long been considered too insensitive to provide useful data in this regard, but ⁴³Ca magic angle spinning (MAS) NMR spectra reported here for synthetic tobermorite and jennite with naturally abundant levels of ⁴³Ca demonstrate that this is a viable approach. We show that spectra with useful signal/noise ratios can be obtained in a reasonable acquisition period (∼2 days) using an H₀ field strength of 21.1 T, 5 mm rotors spinning at a frequency of 5 kHz, and a double frequency sweep preparatory pulse sequence. Tobermorite and jennite produce relatively broad resonances due to their complex structures and structural disorder, however, the chemical shift differences between six-coordinate ⁴³Ca in jennite and seven-coordinate ⁴³Ca in 11 Å tobermorite are large enough that the signals are entirely resolved at this field. These data suggest that signal from ideal tobermorite-like and jennite-like sites in cement C–S–H can most likely be distinguished by ⁴³Ca NMR and that this method will be a powerful approach for studying cement-based ceramic materials in the coming decade.     

Preparation and Optical Properties of Transparent Eu3+:Y3Al5(1−x)Sc5xO12 Ceramics

Using a novel combustion method, Eu-doped Eu:yttrium aluminum garnet (YAG) and Eu:YSAG powders, and transparent Eu:YSAG ceramics were fabricated. The optical properties of these transparent ceramics have been measured, and a reduced peak splitting of Eu³⁺ for ⁵D₀→⁷F₁ and ⁵D₀→⁷F₂ was observed when 10 at.% Al³⁺ was substituted by Sc³⁺. The enhanced symmetry of the Eu sites in YAG lattice, which resulted from the expanded YSAG lattice by Sc³⁺ doping, is the main reason for the reduced peak splitting.     

Synthesis of BaCu(B2O5) Ceramics and their Effect on the Sintering Temperature and Microwave Dielectric Properties of Ba(Zn1/3Nb2/3)O3 Ceramics

BaCu(B₂O₅) ceramics were synthesized and their microwave dielectric properties were investigated. BaCu(B₂O₅) phase was formed at 700°C and melted above 850°C. The BaCu(B₂O₅) ceramic sintered at 810°C had a dielectric constant (ɛ_r) of 7.4, a quality factor ( Q × f ) of 50 000 GHz and a temperature coefficient of resonance frequency (τ_f) of −32 ppm/°C. As the BaCu(B₂O₅) ceramic had a low melting temperature and good microwave dielectric properties, it can be used as a low-temperature sintering aid for microwave dielectric materials for low temperature co-fired ceramic application. When BaCu(B₂O₅) was added to the Ba(Zn_1/3Nb_2/3)O₃ (BZN) ceramic, BZN ceramics were well sintered even at 850°C. BaCu(B₂O₅) existed as a liquid phase during the sintering and assisted the densification of the BZN ceramic. Good microwave dielectric properties of Q × f =16 000 GHz, ɛ_r=35, and τ_f=22.1 ppm/°C were obtained for the BZN+6.0 mol% BaCu(B₂O₅) ceramic sintered at 875°C for 2 h.     

11B and 27Al Nuclear Quadrupole Interactions in SiO2-B2O3-Al2O3-R2O Glass Systems

Quadrupole interactions of ¹¹B and ²⁷Al in SiO₂-B₂O₃-Al₂O₃-R₂O glass systems were investigated to determine the structure of these glasses, which should be amenable to chemical strengthening. The ratio of BO₄ units to BO₃ units approached unity as the R₂O/Al₂O₃ ratio for compounds having fixed B₂O₃ contents approached unity. Nuclear quadrupole coupling constants ( e²Qq/h =2.73 to 2.93 MHz) were measured for the NMR spectra of ¹¹B triangles. The line shapes of ²⁷Al spectra varied with chemical composition, but a few glasses exhibited ²⁷Al line shapes similar to those of the AlO₄ triclusters in SiO₂-Al₂O₃-Na₂O glasses. Compositional trends in the formation of BO₄ and AlO₄ were deduced from the NMR spectra.     

Chemical Degradation of Si3N4-Bonded SiC Sidelining Materials in Aluminum Electrolysis Cells

A thorough analysis of a silicon nitride (Si₃N₄)-bonded SiC sidelining material from a Hall-Heroult electrolysis cell is reported. Phase composition before and after chemical degradation of the material is obtained by quantitative analysis using Rietveld refinement of X-ray diffraction data and chemical analysis. The main degradation products as a result of the oxidation of Si₃N₄ binder phase are Si₂ON₂ in the upper part and Na₂SiO₃ in the lower part of the sidelining. The microstructure of α-Si₃N₄ (needle) and β-Si₃N₄ (shell) as well as the degradation products Si₂ON₂ (fiber) and Na₂SiO₃ (flake) were revealed by electron microprobe analysis. Chemical reactions and degradation mechanisms are proposed based on the presented findings. The degradation in the lower part is more severe than that in the upper part because Na diffusion from the cathode enhances the oxidation of Si₃N₄. The degradation changes the physical properties of Si₃N₄-bonded SiC such as density and porosity.     

Sol-Gel Route to Ferroelectric Layer-Structured Perovskite SrBi2Ta2O9 and SrBi2Nb2O9 Thin Films

Precursors for layer-structured perovskite thin films of SrBi₂Ta₂O₉ (SBT) and SrBi₂Nb₂O₉ (SBN) were prepared by the reactions of a strontium-bismuth double methoxyethoxide and tantalum or niobium methoxyethoxide in methoxyethanol, followed by partial hydrolysis. Several spectroscopic techniques, such as ¹H-, ¹³C-, and ⁹³Nb-NMR (nuclear magnetic resonance), and Fourier-transform infrared spectroscopy were used to analyze the arrangement of the metals and oxygen in the precursor molecules. The precursors contained Sr-O-M (where M is Ta or Nb) bonds (i.e., a strontium is connected to two MO₆ octahedra) and Sr-O-Bi bonds with a bismuth atom bonded to the oxygens of the MO₆ octahedron. The arrangement of metals and oxygens was considered to be similar to the layer-structured perovskite crystal sublattice. As a result, the sol-gel-derived SBT thin films crystallized, by rapid thermal annealing in an oxygen atmosphere below 550°C, and they exhibited preferred (115) orientation. The crystallinity improved and the crystallite size increased with temperature up to 700°C. In the case of SBN thin films, a low heating rate (2°C/min) was necessary for the control of the crystallographic (115) orientation, whereas a rate of 200°C/s (rapid thermal annealing) produced films that exhibited c -axis orientation. The (115) SBT thin film, heated to 700°C, exhibited improved ferroelectric properties.     

Structure, Thermal Behavior, Chemical Durability, and Optical Properties of the Na2O–Al2O3–TiO2–Nb2O5–P2O5 Glass System

The FTIR, Raman, UV-Vis, ³¹P MAS-NMR, DTA, and refractive index measurements have been combined to investigate a series of glasses with the general formula 20Na₂O–5Al₂O₃− x TiO₂–(45− x )Nb₂O₅–30P₂O₅, 15≤ x ≤45. The glass structure, as well as thermal, optical, and chemical durability properties, were then described as functions of the f _Nb/ f _Ti ratio. An increase of the f _Nb/ f _Ti ratio correlates with a decrease in length of the average phosphate chains linked through Nb–O–P and Ti–O–P bonds, with an increase in the glass stability and with increase in the linear refractive indices at 632.8 nm from 1.79 to 1.89. Furthermore, niobium is more effective than titanium in improving chemical durability.     

29Si and 27Al MAS-NMR of NaOH-Activated Blast-Furnace Slag

b²⁹Si and ²⁷Al MAS-NMR were performed on NaOH-activated blast-furnace slag to better characterize the amorphous and poorly crystalline phases which occur in this system. The unreacted glass has a mainly dimeric silicate structure represented by a broad ²⁹Si peak (FWHM = 15 ppm) centered at –74.5 ppm [ Q ¹], with aluminum present exclusively in tetrahedral coordination. Upon reaction with 5M NaOH ( w/s = 0.4), three new ²⁹Si peaks with widths of ca. 2 ppm are formed at -78.5 Q ¹, –81.4 [ Q ²(1Al)J, and -84.3 [ Q ²]. Relative peak areas indicate a mostly dimeric silicate structure for the tobermorite-like C─S─H layers, with roughly a third of the bridging sites occupied by aluminum, and less than 10% by silicon. In addition to the tetrahedrally coordinated aluminum substituted in the C─S─H structure, ²⁷Al MAS-NMR reveals the presence of aluminum in octahedral sites, which is attributed to the aluminate phase (C,M)₄AH₁₃. ²⁹Si results indicate rapid initial consumption of the glass, with roughly a third of the glass reacting within the first day and another third consumed over the following 27 days.     

Electrical Properties of Sr0.7Ba0.3TiO3 Ceramics Doped with Nb2O5, 3Li2O · 2SiO2, and Bi2O3

The electrical properties of Sr_0.5Ba_0.3TiO₃ in the presence of Nb₂O₅ as a donor, 3Li₂O · 2SiO₂ as a sintering agent, and Bi₂O₃ as a dopant have been studied. When the compositions of the ceramics were 1 mol Sr_0.7Ba_0.3TiO₃+ 0.5 mol% Nb₂O₅+ 2 mol% 3Li₂O · 2SiO₂+ 0.2 mol% Bi₂O₃, the ceramics were sintered at 1100°C and exhibited the following characteristics: apparent dielectric constant ɛ, 25000; loss factor tan δ, 2%; insulating resistivity ρ_j, 10¹⁰Ω· cm; variation of dielectric constant with temperature Δɛ/ɛ (−25° to +85°C), +10%, −14%. ɛ and tan δ show only small changes with frequency. The study shows this ceramic can be used in multilayer technology.     

Nature of Alumina in Phosphate Glass: II, Structure of Sodium Alurninophosphate Glass

We have used ²⁷Al and ³¹P magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy and X-ray photoelectron spectroscopy (XPS) to describe quantitatively the relationships between the composition, structure, and properties of glasses in the Na₂O.Al₂O₃.P₂O₅ (NAP) system. In general, the glass properties (evaluated in part I) are most sensitive to changes in Al coordination. ²⁷ Al MAS NMR spectra reveal that octahedrally coordinated Al is most abundant in glasses with O/P ratios less than 3.5, the pyrophosphate structural limit. Tetrahedrally coordinated Al is most abundant in glasses with O/P greater than 3.5. Decreasing Al(OP)₆/Al(OP)₄ ratio generally correlates with decreasing glass transition temperature and refractive index. The compositional dependence of glass structure and properties can be qualitatively understood using a crystal chemical model based on oxygen charge balancing by the different Al and P moieties.     

Extension of Glass-Forming Region in a ZrF4-Based System by Rapid Melt Quenching

It was shown that rapid melt quenching can extend the glass-forming region of a ZrF₄–BaF₂–YF₃–AlF₃ composition considerably. Cooling at a rate of ∼10² K · s⁻¹ prevented glass formation at compositions less than about 25 mol% BaF₂, whereas quenching at a rate of ∼2×10⁶ K · s⁻¹ resulted in glasses with a BaF₂ content as low as about 13 mol%. This high quenching rate was achieved by a specially designed twin-roller apparatus.