Sintering of a Crystallizable CaO-B2O3-SiO2 Glass with Silver

Effects of Ag addition on sintering of a crystallizable CaO-B₂O₃-SiO₂ glass have been investigated at 700°–900°C in different atmospheres. With Ag content increasing in the range of 1–10 vol%, the softening point, the densification, the onset crystallization temperature, and the total amount of crystalline phase formed of the crystallizable glass are reduced when fired in air. A bloating phenomenon is observed when the crystallizable CaO-B₂O₃-SiO₂ glass doped with 1–10 vol% Ag is fired at 700°–900°C for 1–4 h. Fired in N₂ or N₂+ 1% H₂, however, the above phenomena disappear completely. It is thus believed that the diffusion of Ag into the crystallizable glass, which is caused by the oxidation of Ag in air, is the root cause for the above results observed.     

Reaction and Diffusion in Silver-Arsenic Chalcogenide Glass Systems

The diffusion of Ag from the metal or Ag₂Se in amorphous As₂S₃ and As₂Se₃ at 175°C is accompanied by the reduction of As from a valence of 3+ to 2+ or 2+ to 1 + to maintain charge neutrality in the glass. Only Ag⁺ diffuses at this temperature; all other ions are essentially immobile. An amorphous reaction-product phase is formed in the diffusion zone with a composition range of 28.6 to 44.4 at % Ag. The lower limit corresponds to all As cations of 2+ valence (equivalent to amorphous Ag₂As₂S₃); the upper limit, the maximum solubility of Ag in these glasses, corresponds to all As cations of 1 + valence (equivalent to amorphous Ag₁As₂S₃). The diffusivity of Ag in these glasses at 175°C for concentrations of 10 to 35 at.% Ag is
Sulfide 4× 10⁻¹⁴ exp[(+0.23±0.01)(at.% Ag)]cm²/s
Selenide 2' 10⁻¹¹ exp[(+0.14±0.01)(at.% Ag)]cm²/s     

Vacuum Ultraviolet Spectra of Silver in a Borosilicate Glass

Vacuum ultraviolet absorption spectra of silver dissolved in 60 mol% B₂O₃-40 mol% SiO₂ glass in oxygen, nitrogen, and oxygen–nitrogen atmospheres at 1000°, 1100°, and 1200°C were measured. Strong absorption which may be attributed to Ag⁺-complex was observed around 5.5 and 6.5 eV. It is suggested that an Ag⁺-complex/Ag⁰ redox pair exists in the glass and that this pair shows O-type redox behavior.     

Ethene/Ethane (C2H4/C2H6) Separation through an Inorganic–Organic Hybrid Membrane Containing Silver(I) Ions as Olefin Carriers, Using Poly(N-vinylpyrrolidone) as a Mediation Agent

Novel inorganic–organic membranes that contained Ag⁺ ions as olefin carriers were prepared using sol–gel and dip-coating processes. The permeance of the membranes for nitrogen, helium, ethane (C₂H₆), and ethene (C₂H₄) were evaluated using the single-gas permeation method at temperatures of 298, 373, and 423 K. The results showed that the selectivity of the membranes to C₂H₄ against C₂H₆ increased as the measurement temperature increased, because the decomplexation rate of C₂H₄ molecules from Ag⁺ sites is enhanced by increases in the temperature. Fourier transform infrared spectrophotometry of the hybrid membranes and the performance of the membranes at 373 and 423 K indicated that poly( N -vinylpyrrolidone) (PVP) had a role in increasing the flexibility of the inorganic network and also served as a mediation agent to fix Ag⁺ ions in the polymer segments, because of the coordination interaction between the Ag⁺ ions and the PVP.     

Dielectric Properties and Reliability of Zn0.95Mg0.05TiO3+0.25TiO2 MLCCs with Different Pd/Ag Ratios of Electrodes

In order to study the micromechanism of silver migration that influences the dielectric properties and reliability of Zn_0.95Mg_0.05TiO₃+0.25TiO₂ (ZMT") with 1 wt% 3ZnO–B₂O₃ multilayer ceramic capacitors (MLCCs), various silver (Ag)–palladium (Pd) ratios of conductors were used as inner electrodes. It was found that the electrical resistance of a MLCC sample with pure Ag as inner electrodes was degraded drastically to compared with the Ag/Pd inner electrodes at measuring temperatures ranging from 25°C to 175°C. It may be explained that the pure Ag migrates easily into the dielectric layer along the grain boundary during co-firing. The ZMT" MLCCs exhibited increasing dielectric constant and insulation resistance considerably with increasing sintering temperature. Moreover, the results also indicate that Ag diffusion changes the dielectric properties and decreases the breakdown voltage. A ZMT" MLCC with a high Ag content in the inner electrode exhibits poor reliability, and the effect of Ag⁺ migration is markedly enhanced when the activation energy of the ZMT" dielectric is considerably lowered due to the excessive formation of oxygen vacancies and the semiconducting Zn₂TiO₄ phase when Ag⁺ substitutes for Zn²⁺ during co-firing.     

Effect of Neodymium:Yttrium Aluminum Garnet Laser Irradiation on Crystallization in Li2O–Al2O3–SiO2 Glass

A 355-nm neodymium:yttrium aluminum garnet laser, produced by a harmonic generator, was used for the nucleation process in photosensitive glass containing Ag⁺ and Ce³⁺ ions. The pulse width and frequency of the laser were 8 ns and 10 Hz, respectively. Heat treatment was conducted at 570°C for 1 h, following laser irradiation, to produce crystalline growth, after which a LiAlSi₃O₈ crystal phase appeared in the laser-irradiated Li₂O–Al₂O₃–SiO₂ glass. The present study compares the effect of laser-induced nucleation on glass crystallization with that of spontaneous nucleation by heat treatment.     

Characterization of Silver Interdiffusion into (Zn,Mg)TiO3+x:Bi:Sb Multilayer Ceramic Capacitor

In this study, (Zn,Mg)TiO_{3+ x} +Bi₂O₃+Sb₂O₅ multilayer ceramic capacitors (MLCCs) with different proportions of a silver (Ag)–palladium (Pd) mixture acting as the inner electrode were sintered at 925°C for 2 h to evaluate the effect of the inner electrode on reliability. The main results reveal that the lifetime is inversely proportional to the Ag content in the Ag/Pd inner electrode. Ag diffusion into the (Zn,Mg)TiO_{3+ x} +Bi₂O₃+Sb₂O₅ MLCC during cofiring at 925°C for 2 h and Ag migration at 140°C against 200 V are both responsible for the short lifetime of the (Zn,Mg)TiO_{3+ x} +Bi₂O₃+Sb₂O₅ MLCC, particularly the latter factor. A Bi,Sb-rich secondary phase was present at the triple junction and a small amount of Ag was detected from the second phase for a (Zn,Mg)TiO_{3+ x} +Bi₂O₃+Sb₂O₅ MLCC with a high Ag content in the inner electrode of Ag/Pd=99/01. However, this was not the case with a low Ag content in the inner electrode of Ag/Pd=90/10. This means that the Bi,Sb-rich second phase plays an important role in determining the degradation of insulation resistance due to the excessive formation of oxygen vacancies from the reaction of Ag⁺ for Bi³⁺ or Sb⁵⁺ substitution to lower the activation energy of the (Zn,Mg)TiO₃+Bi₂O₃+Sb₂O₅ dielectrics and to enhance markedly the effect of Ag migration.     

Effect of Preparation Temperature on the Lattice Parameter of Nickel Aluminate Spinel

Nickel aluminate spinels were prepared by solid-state reaction. Their lattice parameters ( a ₀) changed with preparation temperature, which was explained by cation distribution, vacancies formation, and cation entrance. When the preparation temperature increased from 1100° to 1200°C, a ₀ decreased with temperature as the result of the uptake of Al₂O₃. After 1200°C, a ₀ increased to temperature, which was attributed to some Ni²⁺ exchange with tetrahedral sites and some vacancies occupancy by Ni²⁺ and Al³⁺.     

Ion Exchange in Alkali Layers of Potassium β -Ferrite ((1 + x)K2O · 11Fe2O3) Single Crystals

The potassium ions in potassium β-ferrite ((1 + x)K₂O ·11Fe₂O₃) crystals were exchanged with Na⁺, Rb⁺, Cs⁺, Ag⁺, NH₄⁺, and H₃O⁺ in molten nitrates or in concentrated H₂SO₄. On the other hand, spinel and hexagonal ferrites were formed by soaking the crystals in the melt of divalent salts. The crystals of K⁺, Rb⁺, and Cs⁺β-ferrites decomposed to form α-Fe₂O₃ at high temperatures of 800° to 1100°C. In addition, H₃O⁺, NH₄⁺, and Ag⁺β-ferrites decomposed to form α-Fe₂O₃ at relatively low temperatures of 350° to 650°C, in accordance with the stabilities of the inserted ions. The electrical properties of some β-ferrites were measured.     

Sol–Gel Synthesis and Characterization of Ag and Au Nanoparticles in SiO2, TiO2, and ZrO2 Thin Films

Silver and gold nanoparticles were synthesized by the sol–gel process in SiO₂, TiO₂, and ZrO₂ thin films. A versatile method, based on the use of coordination chemistry, is presented for stabilizing Ag⁺ and Au³⁺ ions in sol–gel systems. Various ligands of the metal ions were tested, and for each system it was possible to find a suitable ligand capable of stabilizing the metal ions and preventing gold precipitation onto the film surface. Thin films were prepared by spin-coating onto glass or fused silica substrates and then heat-treated at various temperatures in air or H₂ atmosphere for nucleating the metal nanoparticles. The Ag particle size was about 10 nm after heating the SiO₂ film at 600°C and the TiO₂ and ZrO₂ films at 500°C. After heat treatment at 500°C, the Au particle size was 13 and 17 nm in the TiO₂ and ZrO₂ films, respectively. The films were characterized by UV–vis optical absorption spectroscopy and X-ray diffraction, for studying the nucleation and the growth of the metal nanoparticles. The results are discussed with regard to the embedding matrix, the temperature, and the atmosphere of the heat treatment, and it is concluded that crystallization of TiO₂ and ZrO₂ films may hinder the growth of Ag and Au particles.     

Sintering of UN as a Function of Temperature and N2 Pressure

The sintering of uranium mononitride (UN) depends on temperature and the N₂ pressure maintained over the nitride during heat treatment. At a given temperature, an N₂ pressure that maintained the UN in the single-phase region slightly above the phase boundary where the reaction UN→U+½N₂(g) occurred was most effective in accelerating the sintering of single-phase UN. For example, specimens sintered at 1600°C under N₂ pressures of either 1140 or 1.7XlO⁻⁴ torr had essentially identical compositions, but the density of the former was 10.78 g/cm³ (75% of theoretical), whereas that of the latter was 12.20 g/cm³ (85% of theoretical). Results were similar at temperatures up to 2100°C. The X-ray lattice constant of UN sintered at reduced N₂ pressures was slightly larger than that of UN sintered in 1140 torr of N₂. The observed constants ranged from 4.88904 to 4.88991 Å; the combined O+C content varied from 400 to 900 ppm.     

Porous Glass-Ceramics with Bacteriostatic Properties in Silver-Containing Titanium Phosphates: Control of Release of Silver Ions from Glass-Ceramics into Aqueous Solution

Porous glass-ceramics with the surface phase consisting predominantly of AgTi₂(PO₄)₃ crystal and the interior phase of LiTi₂(PO₄)₃ crystal are prepared by exchange of Ag⁺ions for Li⁺ions. In the present work, the release of Ag⁺ ions from glass-ceramics into aqueous solutions was investigated. Exchanged Ag⁺ ions were chemically stable in water. The as-exchanged glass-ceramics released Ag⁺ ions of 3045 equiv/g into phosphate buffer solution containing Na⁺ ions. X-ray diffraction analysis showed that silver-containing titanium phosphate crystalline phase in the glass-ceramics did not deteriorate even by heating at 900°C. The amount released from the heated glass-ceramics into the buffer solution was found to decrease drastically by 1–2 μequiv/g. The heated glass-ceramics showed excellent bacteriostatic properties. Glass-ceramics are expected to be novel bacteriostatic materials which have high thermal resistance and are medically safe.     

Interdiffusion and Association Phenomena in the System NiO-Al2O3

The rate of formation of NiAl₂O₄ by reaction between single crystals of NiO and Al₂O₃ can be described by k = 1.1 × 10⁴ exp (−108,000 ± 5,000/ RT ) cm²/s. In NiO the behavior of D as a function of concentration supports the Lidiard theory of diffusion by impurity-vacancy pairs. A good fit of the theory to the experimental results was obtained by assuming that Al³⁺ ions diffuse as [Al_Ni· V_Ni]'pairs. The diffusion coefficient of pairs, D_p , obeys the equation 6.6 × 10⁻² exp (−54,000 ± 3,000/ RT ) cm²/s. The free energy of association for pairs was calculated to range from 6.5 kcal/mol at 1789°C to 9.0 kcal/mol at 1540°C. The interdiffusion coefficients in the spinel showed a constant small increase with increasing concentration of Al³⁺ dissolved in the spinel.     

Formation of Sm2+ lons in Sol-Gel-Derived Glasses of the System Na2 O-Al2O3-SiO2

Samarium ions (Sm²⁺) incorporated into aluminosilicate glasses by a sol-gel process showed persistent spectral hole burning at room temperature. Gels of the system Na₂O-Al₂O₃SiO₂ synthesized by the hydrolysis of Si(OC₂H₅)₄, Al(OC₄H₉)₃, CH₃ COONa, and SmCl₃·6H₂O 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 Al₂O₃-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 Al₂O₂-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.     

Voltammetric Study of Silver in a Glass Melt

The redox reaction and the oxidation state of silver in a glass melt were studied by cyclic voltammetry and chronopotentiometry between 800° and 1200°C. Silver ions in glass were reduced at a less noble potential than the rest potential of a platinum electrode. A reversible redox reaction of silver in glass was indicated from the analysis of the cyclic voltammogram. An analysis based on the electron transference number revealed that the solubility of reduced silver increased with increasing temperature. Ag⁺/Ag⁰ equilibrium in glass was suggested because the rest potential of the platinum electrode in glass was a mixed potential. No relation was observed between the redox behavior of silver in glass and optical basicity. O-type redox behavior of silver in glass was shown.     

Vapor Pressure, Enthalpy, Evaporation Coefficient, and Enthalpy of Activation of the Beryllium Nitride (Be3N2) Decomposition Reaction

Beryllium nitride (Be₃N₂) vaporizes congruently in the range 1640° to 1960°K by the reaction Be, N₂( c ) = 3Be( g ) + N₂( g ). The equilibrium nitrogen partial pressure, in atmospheres, at the composition for congruent sublimation is given by the expression log P _N2= [(–1.952 ± 0.038) × 10⁴] T ⁻¹+ (6.509 ± 0.207). The measured enthalpy of decomposition (370 ± 5 kcal at 298° K) yields an enthalpy of formation for Be₃N₂( c ) of –136 ± 6 kcal/mole. The upper limit to the evaporation coefficient at 1600° to 2000°K can be set as 10^–4 by comparison of equilibrium data to Langmuir data obtained with a sample of 18% porosity. The apparent enthalpy of activation for the reaction is 409 ± 7 kcal/mole at 1800°K for the porous Langmuir specimen. An expression is developed to predict the temperature dependence of the reduced apparent pressures in Knudsen studies of substances with low evaporation coefficients in terms of the enthalpy of activation. The variation in temperature dependence of the Langmuir measurements and Knudsen measurements with three different-sized orifices is consistent with predictions from this expression.     

Microwave Dielectric Properties of CaTiO3-CaAl1/2Nb1/2O3 Ceramics Doped with Li3NbO4

The microwave dielectric properties of CaTi_{1− x} (Al_1/2Nb_1/2) _x O₃ solid solutions (0.3 ≤ x ≤ 0.7) have been investigated. The sintered samples had perovskite structures similar to CaTiO₃. The substitution of Ti⁴⁺ by Al³⁺/Nb⁵⁺ improved the quality factor Q of the sintered specimens. A small addition of Li₃NbO₄ (about 1 wt%) was found to be very effective for lowering sintering temperature of ceramics from 1450–1500° to 1300°C. The composition with x = 0.5 sintered at 1300°C for 5 h revealed excellent dielectric properties, namely, a dielectric constant (ɛ_r) of 48, a Q × f value of 32 100 GHz, and a temperature coefficient of the resonant frequency (τ_f) of −2 ppm/K. Li₃NbO₄ as a sintering additive had no harmful influence on τ_f of ceramics.     

Synthesis, Properties, and Oxidation of Alumina-Titanium Nitride Composites

Al₂O₃-TiN composites varying from 60 to 66.6 mol% TiN were prepared by an in situ reaction between TiO₂ and AlN. N₂ or O₂ evolution takes place, depending on the composition selected. A pseudobrookite (PB) phase appears in the reaction product, the amount decreasing as the TiO₂:AlN ratio becomes poor in AlN. The in situ reaction product can be pressureless sintered to 94% to 97% theoretical density at 1600°C in N₂. The four-point flexural strength varies from 280 to 430 MPa at room temperature. The fracture toughness is 3 to 4.7 MPa.m^1/2. Oxidation of a 94% dense TiN-Al₂O₃ composite in the temperature range 710° to 1050°C was also studied. A layer of TiO₂ (rutile) protects the composite at 710°C from further oxidation with a weight gain of 0.08 mg/cm² in 90 min. In the temperature range 820° to 1050°C, the initial oxidation kinetics are parabolic, with an activation energy of 216.5 kJ/mol. Linear oxidation kinetics with an activation energy of 113.7 kJ/mol pertain at longer times.     

Kinetics of the UO2-C-N2 Reaction at 1700°C

The mechanism of the reaction of UO₂ with carbon in the presence of N₂ at 1700°C and the rate of formation of the carbonitride product were determined. Uranium carbonitride forms at specific O₂ and N₂ chemical potentials by reactions such as (1) UO₂( s ) + 0.67HCN( g )→UO_1.33N_0.45( s ) + 0.67CO( g ) + 0.11N₂( g ) + 0.335H₂( g ) and (2) UO_1.33N_0.45( s ) + 1.58HCN( g )→UO_0.25N_0.75( s ) + 1.33CO( g ) + 0.79H₂( g ) + 0.64N₂( g ). At P _H2=2×10^-5 atm, HCN formed, permitting a gas-phase transport of reactions not observed in the UO₂-C reaction. Reaction (1) is completed in 0.01 to 0.1 of the time for complete conversion to carbonitride; reaction (2), which proceeds as soon as oxynitride is available, is controlled by solid-state diffusion across the carbonitride layers after they become continuous on the entire specimen. The reaction rates and product compositions depend on the P _N2 and P_CO in the system.     

Effect of Composition on the Mechanical Properties of Aluminosilicate and Borosilicate Glasses

Elastic moduli and fracture toughness were determined for several glasses in the systems soda-alumina-silica, calcia-alumina-silica, and soda-boric oxide-silica. Results for the aluminosilicates are analyzed in terms of Al³⁺:Na⁺ ratios. The mechanical properties do not show maxima or minima at the Al³⁺:Na⁺ ratio of 1, in contrast to conductivity, helium permeability, and refractive index. The moduli and toughness increase with Al³⁺:Na⁺ ratio, which is consistent with increased coherency of the glass network. Glasses which contain B₂O₃ instead of Al₂O₃ have slightly higher moduli but are considerably tougher. The moduli of calcium aluminosilicate glasses are ∼25% greater than sodium aluminosilicates, whereas the fracture toughnesses are similar.