Crystallization of Copper Metaphosphate Glass

The effect of the valence state of copper in copper metaphosphate glass on the crystallization behavior and glass transition temperature has been investigated. The crystallization of copper metaphosphate is initiated from the surface and its main crystalline phase is copper metaphosphate (Cu(PO)₃), independent of the [Cu²⁺]/[Cu_total] ratio in the glass. However, the crystal morphology, the relative crystallization rates, and their temperature dependences are affected by the [Cu²⁺]/[Cu_total] ratio in the glass. The crystal formed in the reduced glass is oriented and needleshaped and less aligned at higher crystallization temperature. On the other hand, the totally oxidized glass crystallizes from all over the surface. The relative crystallization rate of the reduced glass to the totally oxidized glass is large at low temperature, out small at high temperature. The glass transition temperature of the glass increases as the [Cu²⁺]/[Cu_total] ratio is raised. This dependence may be used to explain the relative crystallization rates. It is also found that the atmosphere used during heat treatment does not influence the crystallization of the reduced glass, except for the formation of a very thin CuO surface layer when heated in air.     

Effect of CuO on the Sintering Temperature and Piezoelectric Properties of (Na0.5K0.5)NbO3 Lead-Free Piezoelectric Ceramics

When a small amount of CuO was added to (Na_0.5K_0.5)NbO₃ (NKN) ceramics sintered at 960°C for 2 h, a dense microstructure with increased grains was developed, probably due to liquid-phase sintering. The Curie temperature slightly increased when CuO exceeded 1.5 mol%. The Cu²⁺ ion was considered to have replaced the Nb⁵⁺ ion and acted as a hardener, which increased the E _c and Q _m values of the NKN ceramics. High piezoelectric properties of k _p=0.37, Q _m=844, and ɛ₃ ^T /ɛ₀=229 were obtained from the specimen containing 1.5 mol% of CuO sintered at 960°C for 2 h.     

Zinc Tellurite Glasses

Glass formation was observed in the system ZnO-TeO₂ in mixtures containing 20 to 40 mole % ZnO. Softening occurred at 350°C and the glasses crystallized at 400°C. High dielectric constants (ca. 20) and high electrical resistivities (ca. 10¹¹ ohm-cm⁻¹) were measured. The zinc tellurite glasses have a higher density and refractive index and are considerably softer than silicate glasses. The optical transmission range was between 0.38 and 6.6μ with two absorption bands in the infrared. Spectra of Cu²⁺ and Nd³⁺ doped samples are also given.     

Role of Copper Ions in Low-Melting Solder Glasses

Controlled melting conditions for Cu-containing solder glasses yielded a variety of Cu⁺/Cu²⁺ ratios from a single glass starting composition. Measurements of softening point, thermal expansion, chemical durability, plus chemical analysis revealed that the well-known viscosity effect of adding copper oxide to solder glasses is caused primarily by the Cu⁺ ion; Cu²⁺ plays a minor role, if any.     

Stannous-Stannic Equilibrium in Molten Binary Alkali Silicate and Ternary Silicate Glasses

The stannous-stannic equilibrium in binary alkali silicate and ternary silicate glasses was studied by equilibrating glassmelts with air at 1400°C. The Sn²⁺-Sn⁴⁺ equilibrium shifts more toward the oxidized state with increasing ionic radii of the alkali ions or with increasing concentration of the alkali ions in the same series of glasses. The slope of the straight lines obtained on plotting log (Sn⁴⁺)/(Sn²⁺)( pO₂ )^n/2 vs mol% R₂O increased in the order Li→Na→K. In ternary silicate glasses having the base glass composition 20Na₂O·10RO·70SiO₂, the Sn²⁺-Sn⁴⁺ equilibrium shifts more toward the reduced state, with increasing bond strength between the divalent cations and the nonbridging oxygens. With increasing temperature, the equilibrium shifts more toward the reduced state.     

Kinetic Study of Cu+−Cu2+ Equilibrium in Sodium Na2O−Al2O3−B2O3 Glass

The Cu⁺−Cu²⁺ equilibrium in sodium aluminoborate glass with an air atmosphere was studied at 950°, 1050°, and 1150°C. Equations suggested to represent the equilibrium reaction between oxidized and reduced species and oxygen were critically examined. An equation to represent the Cu⁺−Cu²⁺ equilibrium reaction was suggested. The reaction was observed to follow first-order kinetics. Enthalpy of the reaction was—12.5 kcal/mol.     

Low-Temperature Sintering of Alumina with Liquid-Forming Additives

Simultaneous application of colloidal processing and liquid-forming additives to alumina resulted in a sintered density of >99% in 1 h at a temperature as low as 1070°C for a commercial high-purity alumina powder at a total dopant level of 2 mol%. The additives were 0.9% CuO + 0.9% TiO₂+ 0.1% B₂O₃+ 0.1% MgO. At higher temperatures or after prolonged sintering, the doped alumina ceramic developed a duplex microstructure containing large elongated grains and exhibited a relatively high fracture toughness of ∼ 3.8 MPa · m^1/2 as compared to a value of ∼ 2.6 MPa · m^1/2 for the undoped alumina.     

Effect of a liquid Phase on Superplasticity of 2-moI%-Y203-StabiIlzed Tetragonal Zirconla Polycrystals

A small addition of CuO to 2-mol%-Y₂O₃-stabilized tetragonal zirconia polycrystals significantly enhances superplasticity by forming an amorhous grain-boundary phase containing primarily Cu⁺, Y³⁺, Zr⁴⁺, and O²⁻. This phase apparently melts at around 1130°C, but it already provides a fast diffusion path even below the melting temperature. There are abrupt changes in stress exponent, activation energy, and grain size exponent across the melting temperature. Superplasticity is diffusion-controlled below the melting temperature and is interfaced-controlled above that.     

Cation Effects on Anion Distributions in Aluminophosphate Glasses

Alkali aluminophosphate glasses, including those in the system x Al₂O₃·(1− x )CsPO₃ (0 ≤ x ≤ 0.25), were examined by high-performance liquid chromatography (HPLC), infrared (IR), and ²⁷Al magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopies. Phosphate anions become progressively shorter with the addition of alumina to a metaphosphate glass. Al³⁺ ions are initially incorporated into the structure in octahedral sites, but the average Al coordination number (CN) decreases with increasing alumina content and tetrahedral species are the preferred moiety when [O]/[P] > 3.5. Al[4] sites appear to be associated with monophosphate (Q⁰) anions. The role of modifier size on aluminophosphate structure is investigated. At low alumina content (<15 mol%), the disproportionation of pyrophosphate anions into triphosphate and orthophosphate anions is responsible for the lower average Al CN of cesium aluminophosphate glasses compared with sodium aluminophosphate glasses.     

Electrical Properties of Superionic Conducting Glasses in the Pseudobinary System CuI-Cu2MoO4

Cu⁺-ion-conducting glasses were prepared in the pseudo-binary system CuI-Cu₂MoO₄. These glasses have high ionic conductivities at room temperature in the range 10⁻¹ to 10° S·m⁻¹, which are 10 to 20 times greater than those of the Ag⁺-ion-conducting glasses with the same iodide contents in the system AgI-Ag₂MoO₄. The conductivities increase with increasing CuI content. The increase in the conductivity can be explained in terms of a decrease in the activation energy for conduction. The electronic conductivity was measured by the Wagner polarization method and indicates that the transport number of Cu⁺ ions in those glasses is 0.9996 and larger.     

Polymer Mixtures in Na2O.Sb2O3.GeO2 Glasses

Ternary Na₂O.Sb₂O₃.GeO₂ glasses (with various [Na]/[Na + Sb] ratios) that contained ≥65 mol% GeO₂ were prepared. Their densities (volumes), refractive indices, and infrared spectra were determined and their colors noted. The ternary glasses with ≥88 mol% GeO₂ exhibit nearly additive volumes, refractivities, and frequencies for the main Ge-O vibration. Ternary glasses with lesser amounts of GeO₂ exhibit a variety of behaviors, depending on the [Na]/[Na + Sb] ratio. Small amounts of Sb₂O₃ cause significant volume and refraction deviations, as well as changes in ν_Ge-O, that can be associated with gradual elimination of GeO₆ octahedra. All the information supports a model for the glasses with 65 to 88 mol% GeO₂ that involves a degree of depolymerization that is greater when Na₂O and Sb₂O₃ are present together than when either is present alone.     

Color and Selected Properties of PbO─BiO1.5─GaO1.5 Glasses

The density; molar volume; thermal expansion coefficient; dissolution rate in water, HC1, and NaOH; glass transition and crystallization temperatures; and the absorption edge in the ultraviolet-visible and infrared were measured for PbO─BiO1.5─GaO1.5 glasses. The range of compositions investigated was x PbO (100 − (x + y) )BiO_1.5. yGaO_1.5 for x between 20 and 60 cat% and y of 20, 25, 30, and 35 cat%. The glass-forming tendency increased with increased GaO_1.5 and decreased with increased PbO or BiO_1.5. The compositional dependence of these properties was consistent with the weight, size, charge, and bond strength of the cations. The Ga^{3 +} ions in these glasses are believed to act primarily as network-forming cations, whereas the majority of the Bi³⁺ and Pb²⁺ ions behave as network-modifying cations. It is suggested that a small friction of the lead ions are present as Pb⁴⁺. Depending upon melting conditions, these glasses ranged in color from brown to yellow. Various attempts, including containerless melting, were made to obtain colorless glasses, but no conditions were found which totally eliminated the color. The least color (pale yellow) was obtained when the glasses were melted in an air or nitrogen atmosphere in an alumina or gold crucible.     

Electrical Resistivity of Titanium-Containing Glasses

Titanium-containing glasses were prepared by fusion of a base glass (BaO·B₂O₃SiO₂) and TiO₂ and/or Ti₂O₃ in Ar. Their resistivities did not vary with melting time and temperature. Interaction of Ti⁴⁺ and Ti³⁺ in the glasses was deduced by spectroscopy, but the valence states in the batch compositions were preserved in the glasses, according to the chemical analysis. Glasses containing either Ti⁴⁺ or Ti³⁺ had very high resistivities, whereas the glass prepared by melting a mixture of a Ti⁴⁺-containing and a Ti³⁺-containing glass had much lower resistivity. All results confirmed the possibility of controlling the resistivity by batch composition for these glasses.     

Effect of Oxidation State of Iron on Phase Separation in Sodium Silicate Glasses

The effect of the oxidation state of iron on the phase separation of x Na₂O·(100 – x )SiO₂ glasses, x = 18.56 and 13, containing 0.5 mol% Fe₂O₃ was studied. The oxidation state of iron in the glasses was varied by changing the melting conditions, such as melting temperature and melting atmosphere. The oxidation states of the iron ion were determined using colorimetric and UV–VIS–NIR spectrophotometric methods, and a comparison was made between the results obtained using these two methods. Immiscibility temperatures of the glasses were determined using opalescence and clearing methods. The immiscibility temperature of the sodium silicate binary glasses decreased ∼25°C with the addition of 0.5 mol% Fe₂O₃. The immiscibility temperature of the doped glasses increased slightly with increased concentration of Fe²⁺ ion in the glass. The prediction of immiscibility tendency on the addition of a minor amount of third component was made using models proposed by Tomozawa and Obara and Nakagawa and Izumitani. The Tomozawa and Obara model showed good agreement with measured immiscibility values.     

Copper ⇌ Alkali Ion Exchange of Alkali Aluminosilicate Glasses in Copper-Containing Molten Salt: II, Divalent Copper Salts, CuCl2 and CuSO4

The ion-exchange mechanism between copper and alkali ions, when 20R₂O · 10Al₂O₃· 70SiO₂ (R = Li, Na, and K) glasses are immersed in divalent copper-containing molten salts in air and nitrogen at 550°C, has been investigated. In molten CuCl₂, the ion-exchange behavior in both air and nitrogen was very close to that in molten CuCl in air reported previously. This is explained by assuming that CuCl₂ decomposes into CuCl and Cl₂ at 550°C and the Cu⁺ ions thus formed mainly diffuse in glasses to replace alkali ions, where Cl₂ acts as an oxidizing agent just like oxygen. In the case of molten CuSO₄─₂SO₄, a small amount of Cu⁺ which is present in the molten state plays a primary role in the Cu ⇌ R⁺ ion exchange process, although the contribution of direct Cu²⁺⇌ 2R⁺ ion exchange cannot be ignored.     

Concentrations of Residual Carbonate Ions in the Bi-Sr-Ca-Cu-O Glasses

It was found that the IR absorption bands appearing at 600 to 1600 cm⁻¹, which had been previously assigned to the fundamental vibrations of [BiO₃] or [BiO₆] polyhedra, are due to residual carbonate ions (CO²⁻₃) dissolved in Bi-Sr-Ca-Cu-O glasses. The concentrations of the remaining CO²⁻₃ in the Bi_2.2Sr₂Ca₁Cu₂O _x glasses that melted at 1100° and 1400°C are 170 × 10⁻⁵ mol/cm³ (3.3 mol%) and 3.2 × 10⁻⁵ mol/cm³ (0.25 mol%), respectively. The apparent activation energy for the dissociation of the carbonates was approximately 220 kJ/mol. The CO²⁻₃ content in the precursor glasses did not significantly affect the superconducting properties of the resulting glass–ceramics.     

Preparation by a Sol-Gel Process of Borosilicate Glasses Containing Microcrystals of Tellurium and Zinc Telluride

Borosilicate glasses, 5B₂O₃· 95SiO₂ (mol%), containing TeO₂ and ZnO nominally equivalent to 10 wt% Te and ZnTe were prepared by a solgel method from Si(OC₂H₅)₄, B(OCH₃)₃, H₆TeO₆, and Zn(NO₃)₂. A study by electron spectroscopy for chemical analysis (ESCA) showed that glasses heated at high temperature (450°C) in air contained both Te⁶⁺ and Te⁴⁺ ions on the surface layer, but that mainly Te⁴⁺ ions occurred inside the bulk glass. When solgel-derived borosilicate glasses containing the TeO₂ compound were reduced at elevated temperature in a hydrogen atmosphere, Te crystallites ranging in size from 4 to 15 nm were produced at a lower temperature, between 200° and 250°C. The absorption edge moved from the infrared to the visible wavelength region as the particle size decreased to about 4 nm. For glasses containing both TeO₂ and ZnO, ZnTe crystallites formed at high temperature—over 300°C—and existed along with the Te phase.     

Copper ⇌ Alkali Ion Exchange of Alkali Aluminosillcate Glasses in Copper-Containing Molten Salt: I, Monovalent Copper Salt, CuCl

Cu⁺⇌ R⁺ (R = Li, Na, and K) ion exchange experiments were conducted for 20R₂O·10Al₂O₃·70SiO₂ glasses in molten CuCl at 550°C in air and nitrogen atmospheres. The depth profiles of the copper incorporated into glasses were determined with an electron microprobe X-ray analyzer. The total amount of diffusing copper, M _t, strongly depended on the type of alkali ion in the glass and the ion-exchange atmosphere; i.e., M _t increased with increasing cationic size in the order Li < Na < K and M _t was greater in air than in nitrogen. The Cu ⇌ R⁺ ion exchange kinetics are discussed in detail.     

Optical and Magnetic Properties of Some Transition Metal Ions in Barium Phosphate Glass

In barium phosphate glass containing first-row transition metal ions, the ions appear to possess normal oxidation states: Cr³⁺, Mn³⁺, Fe^2+,3+, Co²⁺, Ni²⁺, and Cu²⁺. Room temperature and 77°K spectra for Cr³⁺-, Mn³⁺-, Fe^2+,3+-, Ni²⁺-, and Cu²⁺-containing glasses can be interpreted, on the, basis of octahedrally coordinated metal ions, whereas the spectrum of the Co²⁺ glass correlates with a tetrahedrally coordinated metal ion. Magnetic moments for the glasses are similar to those for the spin-only values of the various metal ions.     

Colloidal Processing and Ionic Conductivity of Fine-Grained Cupric-Oxide-Doped Tetragonal Zirconia

CuO-doped tetragonal ZrO₂ (3-mol%-Y₂O₃-doped tetragonal zirconia, 3Y-TZ) green bodies were consolidated from zirconia slurries with Cu²⁺ by a pressure filtration method. The slurries were prepared by dispersing 3Y-TZ powder in a solution of [NH₄OH + NH₃NO₃] = 0.1 M at pH 11 and adding an appropriate amount of Cu(NO₃)·3H₂O solution. Green bodies with narrow pore-size distribution were obtained after cold isostatically pressing the pressure-filtrated bodies. Small amounts of CuO-doped samples were densified fully at 1200°C. The size of a grain of 0.16-mol%-CuO-doped 3Y-TZ sintered at 1200°C was 84 nm. Bulk and grain-boundary conductivities are measured by a complex impedance method. The bulk conductivity of the CuO-doped 3Y-TZ was almost equal to the undoped one, but the grain-boundary conductivity decreased with CuO addition.