Improved Aging Characteristics of NTC Thermistor Thin Films Fabricated by a Hybrid Sol–Gel–MOD Process

Negative temperature coefficient thermistor oxide thin films with improved aging characteristics are described. Better thermal stability has been achieved by incorporating sol–gel techniques with metallo-organic decomposition methods. A compositional range was identified whereby borosilicate may incorporate into the thermistor oxides, forming nanocomposites showing thermistor electrical characteristics. Thermistor thin films, with composition Ni_0.48Co_0.24Cu_0.6Mn_1.68O₄·0.22SiO₂·0.15B₂O₃ were deposited onto glass substrates from a solution containing organic transition metal salts, tetraethyl orthosilicate and triethyl borate. Electrical resistance measurements verified characteristic thermistor behavior. Nanocomposite thin films exhibited a factor of four improvement as compared with pure oxides after aging at 150°C for 500 h.     

Chemical Durability of Fluoride Glasses: III, The Effect of Solution pH

The aqueous corrosion behavior of glasses from two heavy-metal fluoride families (ZrF₄-based and BaF₂-ThF₄-based) was studied as a function of controlled solution pH and of glass composition. Leach test results demonstrate a profound pH dependence of corrosion over the range pH 2 to 13. Whereas the glasses readily undergo congruent matrix dissolution in acidic media, they exhibit a marked increase in chemical durability in neutral and basic solutions, with the optimum aqueous environment occurring near pH 7. Results of this study are discussed and compared with results reported earlier for leach tests of these two compositional families in unbuffered de-ionized water. In addition, several testing methods, both static and dynamic, are described and point to the importance of appropriate test selection in predicting the corrosion resistance of these glasses over prolonged periods.     

Surface Crystal Formation During Acid Corrosion of Phosphate-Doped Lead Silicate Glass

The effect of small P₂O₅ additions on the acid corrosion behavior of lead silicate glass was studied at 22°C. Crystals of penta-lead phosphosilicate, a phase heretofore synthesized only by high-temperature melt techniques, formed on the surface of the phosphate-doped glass during the corrosion process. No crystals were observed to form on the pure lead silicate glass. Crystallization appears to result from the controlled release of phosphorus and lead at the glass surface and/or from the reactive catalytic properties of a silica gel surface film. Apparent lead diffusion rates into the acid solution for the phosphate-doped lead silicate glass are much less (by a factor of 11,3) than for the pure lead silicate glass. Application of these findings is suggested in two areas: formulation of low cation-release glass and glaze compositions and the synthesis of high-temperature phases in aqueous solution at ambient temperatures.     

Chemical Durability of Na2O-K2O-CaO-SiO2 Glasses

The mixed-alkali effect on chemical durability was evaluated for bulk and powdered Na₂O-K₂O-CaO-SiO₂ glasses. Two contributions to this effect are discussed, i.e. those of glass structure and corrosion solution. The magnitude of the mixed-alkali effect depends on the pH of the corroding solution. For pH<9, alkali-ion leaching is the major mode of glass corrosion, and the mixed-alkali effect is large. However, for pH≥9 congruent glass dissolution is the rate-controlling corrosion mechanism, and the effect is diminished. When ion exchange is the rate-controlling corrosion mechanism the magnitude of the mixed-alkali effect depends on the extent of reaction. Since the kinetics of corrosion are influenced by the ratio of glass surface area to solution volume ( SA/V ), results obtained when this ratio is large may be misleading if extrapolated to smaller ratios. Physical evidence of the mixed-alkali effect in bulk glasses was obtained using scanning electron microscopy and ir reflection spectroscopy.     

Hot Corrosion of Silica

The high-temperature corrosion of bulk silica glass was studied in pure oxygen and in SO₃-containing oxygen atmospheres in the presence of liquid sulfate deposits at temperatures of 700° and 1000°C. No reaction and devitrification were observed without Na₂SO₄ on the surface. The wetting of the silica by the sulfate, the tendency toward basic fluxing, and the crystallization of the silica incrased with the activity of Na₂O. The most extensive degradation of vitreous silica occurred by crystallization, and the resulting spalling under basic conditions and thermal cycling at basic conditions were parabolic. This behavior is explained by a model in which the crystallization is controlled by sodium at the glass-crystal interface and its diffusion into the glass. This sodium diffuses into the glass before crystallization and is swept ahead of the crystallization front.     

Preparation and Properties of Heavy-Metal Fluoride Glasses Containing Ytterbium or Lutetium

Beginning with a 19BaF₂−27ZnF₂−27YbF₃−27ThF₄ (mol%) base glass, compositional modifications were made to improve optical properties and glass-forming ability. Replacement of YbF₃ by LuF₃ removed a strong near-ir electronic absorption band, and small additions of LiF and NaF improved glass quality. The multicomponent BaF₂/ThF₄ glasses had higher refractive indices and lower expansion coefficients than fluorozirconate and fluorohafnate glasses. In the 6 to 10 μm region, these materials exhibit absorption coefficients an order of magnitude lower than those reported for other heavy-metal fluoride glasses.     

Low-Silica Glasses Based on Calcium Aluminates

An exploratory study of the effects of compositional variation on glass formation in low-silica aluminate compositions revealed that CaO is essential for glass formation at ordinary quenching rates. Other oxides, such as Li₂O, MgO, BaO, ZnO, Na₂O, K₂O, BeO, B₂O₃, and PbO, can be present in the glass in limited amounts (in some cases up to 30 mol%). A necessary, but insufficient, condition for easy glass formation is that the ratio of oxygen ions to network-forming cations (assumed to be Si⁴⁺ and Al³⁺) be ∼2.5. The glass-forming compositions were also characterized by liquidus temperatures below ∼1500°C (2732°F). Young's modulus ranged from 13.0 to 17.8×10⁶ psi. Glasses containing network-modifying cations with high field strengths generally had the higher moduli. Strength (420,000 to 650,000 psi in 0.3-mil fibers), static fatigue, viscosity, annealing, and surface tension were studied to a limited extent for the composition (in mol%) 30Al₂O₃-4SiO₂-60CaO-6MgO.     

Thermodynamics of Arsenic in Glass

Vapor pressures of arsenic trioxide over glass have been determined. From these results, together with analytical data of trivalent and pentavalent arsenic in the glass and the oxygen pressure, the free energies of solution of arsenic trioxide and arsenic pentoxide have been calculated. In a similar way the free energy of formation of Na₄As₂O₇ from the oxides has been determined for comparison.     

Mechanical Behavior of a Borosilicate Glass Under Aqueous Corrosion

In France, fission products are being vitrified for a possible final geological disposal. Under disposal conditions, corrosion of the glass by groundwater as well as stress corrosion because of stresses occurring at surface flaws cannot be excluded. Within this framework, the mechanical behavior of the French simulated nuclear waste glass SON68 was studied by Vickers indentation and fracture experiments in air and in a corrosive solution. The glass was corroded at 90°C in a solution enriched with Si, B, and Na. The results showed that the glass corrosion enhances the cracks propagation relative to experiments in air. The indentation fracture toughness ( K _{I C} ) obtained using a four-point bending test showed that the K _{I C} of the glass decreased with increasing corrosion time.     

Compositional Inhomogeneity in Li- and Ta-Modified (K, Na)NbO3 Ceramics

Compositional inhomogeneity is examined in Li- and Ta-modified potassium sodium niobate (K,Na)NbO₃ perovskite ceramics. The inhomogeneous distribution of the A-site (K and Na) and B-site (Nb and Ta) cations is found to be correlative. The inhomogeneity could not be eliminated by prolonged high-temperature annealing in samples prepared by direct mixing of alkaline carbonates and Ta and Nb oxides. In contrast, the precursor method, where a (Nb _x Ta_{1− x} )₂O₅ solid solution was first formed, led to a considerably improved compositional homogeneity and appreciably enhanced dielectric, ferroelectric, and piezoelectric properties. Our results suggest that more attention needs to be paid toward controlling the compositional fluctuation of this complex solid solution system.     

Early Stages of Calcium Phosphate Formation on Bioactive Borosilicate Glass in Aqueous Phosphate Solution

The conversion of bioactive glass to a calcium phosphate material, typically hydroxyapatite (HA), by solution–precipitation reactions in aqueous phosphate solution, has been commonly reported. This paper describes the structural and compositional characteristics of the calcium phosphate material formed during the early-stage conversion (<5 h) of a borosilicate glass (designated H12) in aqueous phosphate solution. Disks of H12 glass were reacted with 0.25 M K₂HPO₄ solution with a starting pH=7.0 at 37°C. The structure and composition of the product layer were characterized using thin film X-ray diffraction, scanning electron microscopy, and Fourier transform infrared reflectance spectroscopy. For reaction times <5 h, the results indicated the formation of brushite (CaHPO₄·2H₂O) with coarse, plate-like crystals. In comparison, the formation of HA with small needle-like crystals was found at later times. This early-stage formation of brushite has not been reported in previous studies of converting bioactive silicate and borate glasses in aqueous phosphate solution.     

Decomposition of Ruthenium Oxides in Lead Borosilicate Glass

Behaviors of apparent phase changes of Ru-containing oxides in lead borosilicate glass at high temperature have been investigated using X-ray diffraction and transmission electron microscopy in application to thick-film resistors. During firing of thick films containing Ru oxide powder and lead borosilicate glass frits, apparent phase changes of Ru oxides have been found to occur both ways between ruthenium dioxide and lead ruthenate pyrochlore via decomposition of one phase in glass and subsequent formation of the other. The formation of pyrochlore occurs in a lead-rich form, Pb₂(Ru_{2− x} Pb _x )O_6.5, whereas the formation of RuO₂ is characterized by a platelike morphology instead of initial globular morphology. A general tendency is observed that RuO₂ is stable in low-PbO glass compositions and at high temperatures, while Pb₂(Ru_{2− x} Pb _x )O_6.5 is stable in high-PbO glass compositions and at low temperatures, with the implication that the stability of these phases is dictated by the chemical activity of PbO in the glass melt.     

Conversion of Bioactive Borosilicate Glass to Multilayered Hydroxyapatite in Dilute Phosphate Solution

The conversion of a bioactive borosilicate glass in aqueous phosphate solution was observed to produce vastly different reaction kinetics and hydroxyapatite (HA) microstructures, depending on whether the glass was reacted continuously or intermittently in the solution. Particles (150–300 μm) of a borosilicate glass (designated H12) were reacted continuously or intermittently in 0.25 M K₂HPO₄ solution with a starting pH value of 7.0 at 37°C. The conversion kinetics of the glass particles to HA were determined from weight loss measurements. Structural and compositional changes resulting from the conversion reaction were characterized using scanning electron microscopy, X-ray diffraction, energy-dispersive X-ray analysis, and Fourier transform infrared spectroscopy. For conversion experiments carried out intermittently (12–24 h intervals, followed by drying), faster reaction kinetics and a unique multilayered microstructure, consisting of alternating layers of HA and an amorphous SiO₂-rich material with nearly uniform thickness (2–3 μm), were observed. On the other hand, particles reacted continuously in the phosphate solution for the same total time converted more slowly and produced a single HA layer. The kinetics and mechanism of forming HA under the intermittent and continuous reaction conditions are described and compared with those for bioactive silicate and borate glasses studied in previous work.     

Thermochemistry and Aqueous Durability of Ternary Glass Forming Ba-Titanosilicates: Fresnoite (Ba2TiSi2O8) and Ba-Titanite (BaTiSiO5)

Barium titanosilicates are possible oxide forms for the immobilization of short-lived fission products in radioactive waste. Ba₂TiSi₂O₈ (fresnoite) and BaTiSiO₅ (Ba-titanite) samples were prepared by a solid-state synthesis. The enthalpies of formation of Ba₂TiSi₂O₈ crystal and glass at 25°C and of BaTiSiO₅ glass were obtained from drop solution calorimetry in a molten lead borate (2PbO–B₂O₃) solvent at 701°C. The enthalpy of formation for fresnoite composition samples from constituent oxides was exothermic and became more exothermic with increasing crystallinity. Differential scanning calorimetry revealed that the crystallization rate of the fresnoite glasses increased with increasing devitrification. A modified Product Consistency Test-Procedure B (PCT-B) was used to collect solubility data on the fresnoite and titanate phases. The tests suggest that both glassy and crystalline fresnoite exhibit favorable aqueous stability and should be explored further as radioactive waste forms for long-term storage.     

Redox Equilibria of Multivalent Ions in Silicate Glasses

Experimental studies were made on the compositional dependence of the redox equilibrium of Eu in synthetic silicate liquids, together with an empirical model describing the observed compositional dependence. Electron paramagnetic resonance (EPR) was used to measure the concentration ratio of Eu²⁺ to Eu³⁺ in various glasses formed by rapidly quenching silicate liquids. The compositional field studied comprised mixtures of SiO₂, TiO₂, Al₂O₃, CaO, MgO, and Na₂O. The proposed model describes the Eu²⁺/Eu³⁺ ratio over the entire compositional field in terms of parameters easily related to each glass composition. The general applicability and utility of the model is further demonstrated by its application to the Fe²⁺-Fe³⁺, Ce³⁺-Ce⁴⁺, and Cr³⁺-Cr⁶⁺ redox reactions in binary alkali oxide silicate glasses of Li, Na, and K.     

Rare-Earth Aluminosilicate Glasses

Rare-earth aluminosilicate glasses of the general formula 20R₂O₃· 20Al₂O₃· 60SiO₂ have been formed for 10 of the 14 possible rare-earth oxides. Two series of "mixed-rare-earth" glasses were also formed (Nd/Er and Nd/Y). These glasses exhibit exceptionally high glass transformation temperatures, moderate thermal expansion coefficients, and refractive indices of approximately 1.65. The glass transformation temperature and thermal expansion coefficients vary linearly with the field strength of the rare-earth ion. No evidence of a "mixed-rare-earth effect" was observed. MAS-NMR indicates that the aluminum ions are tetrahedrally coordinated in at least some of these glasses.     

Dielectric Losses of Some Simple Ternary Silicate Glasses

The effect on alkali ion mobility of compositional changes in simple glasses was investigated by observing the dielectric loss behavior in a number of ternary glass systems, formed by adding increasing amounts of various third components to potassia-silica and soda-silica base glasses. Oxides of barium, strontium, calcium, cadmium, lead, magnesium, zinc, aluminum, boron, tin, zirconium, titanium, and silicon were introduced. Tan δ values were determined at room temperature and at a frequency of 1 kc. per second. Na⁺ ion mobility was found to be profoundly influenced by the type and amount of third component present. RO oxides decreased tan δ by amounts which appear to bear some relation to the size of the cation introduced. Tan δ curves for the MgO and ZnO series were unique in that each was characterized by a pronounced minimum and maximum. Curves for SnO₂, Al₂O₃, and ZrO₂ additions passed through a minimum and in the latter two cases rose to tan δ values greater than that of the base glass itself. Curves for the series containing B₂O₃ and TiO₂ continued to lower values throughout the range of compositions studied. The characteristic shapes of the loss curves are discussed with reference to the roles assumed by the introduced cations.     

Corrosion Behavior of Alumina Ceramics in Caustic Alkaline Solutions at High Temperatures

The corrosion rate and changes in the microstructure and fracture strength of alumina ceramics (93.0% Al₂O₃ and 99.5% Al₂O₃) were studied in 0.1 m to 25 m NaOH solutions at 150°C to 200°C, where m = mol/(kg of H₂O). The attack of the caustic alkaline solution started at the grain boundaries. Consequently, the corrosion resistance increased with decreasing SiO₂ content in Al₂O₃ ceramics, and the corrosion resistance of 99.5% pure Al₂O₃ was similar to that of Si₃N₄ ceramics. Since large pits are formed by corrosion, the surface area increased first and the apparent corrosion rate increased with time in the initial stage of the corrosion. The corrosion rate of Al₂O₃ increased linearly with increasing NaOH concentration, and the activation energy was 102 kJ/mol. The fracture strength of corroded Al₂O₃ decreased monotonically as the degree of dissolution of alumina increased.     

Interaction of Yttria with Uranium Fluoride Gases (UFn, n= 4, 6) at High Temperatures

The corrosion mechanism and microstructural characteristics of yttria (Y₂O₃) exposed to uranium hexafluoride (UF₄) and uranium tetrafluoride gases at temperatures above 900°C were investigated. Processed yttria samples were exposed for times ranging from 5 to 40 min. A weight increase was observed after each test exposure. An outer corrosion scale composed of UO₂ and YF₃, and an inner corrosion layer of YF₃, were observed following the UF₆ reaction at nearly 1200 K. During the UF₄ exposure, an outer layer containing a liquid mixture of fluoride, oxygen, yttrium, uranium compounds, a secondary reaction layer of UO₂ followed by an inner layer composed of a solution of Y₂O₃ and YF₃, possibly in the form of YOF inner layer, were observed. It was found that the corrosion process is controlled by the diffusion which is evidenced by the parabolic growth rate of the secondary layer. After completion of the solidification process, the formation of a eutectic region and dendrites were observed throughout the outer scale. In general, at temperatures above 1173 K, high corrosion rates were observed, and yttria did not appear to be a viable containment material for UF₄ and UF₆.     

Molten Glass Corrosion Resistance of Immersed Combustion-Heating Tube Materials in Soda-Lime-Silicate Glass

The corrosion resistance of molybdenum, molybdenum disilicide, and a SiC_(p)/Al₂O₃ composite to molten soda-lime-silicate glass was studied. The ASTM-C621–84 corrosion test method was modified because of inherent inaccuracies in the method and Si attack of platinum crucibles. Specimen-glass interfacial regions were characterized using XRD, SEM, and EDS. After 48 h of exposure at 1565°C, the half-down corrosion recessions of Mo, MoSi₂, and SiC_(P)/Al₂O₃ were 0.11, 0.316, and 0.26 mm, respectively. Mo oxidized to form a MoO₂ surface scale which cracked, allowing glass seepage and further oxidation. Silicon was leached out of MoSi₂ into the glass, leaving a Mo₅Si₃ interface and particles of Mo near the interface. For the SiC_(P)/Al₂O₃ composite, bubbles observed at the interfacial regions formed from oxidation of SiC to form CO. Thermodynamic modeling corroborated these experimental observations.