Properties of Sm2O3─Al2O3─SiO2 Glasses for In Vivo Applications

The compositional range for glass formation below 1600°C in the Sm₂O₃─Al₂O₃─SiO₂ system is (9–25)Sm₂O₃─(10–35)Al₂O₃─(40–75)SiO₂ (mol%). Selected properties of the Sm₂O₃─Al₂O₃─SiO₂ (SmAS) glasses were evaluated as a function of composition. The density, refractive index, microhardness, and thermal expansion coefficient increased as the Sm₂O₃ content increased from 9 to 25 mol%, the values exceeding those for fused silica. The dissolution rate in 1 N HCl and in deionized water increased with increasing Sm₂O₃ content and with increasing temperature to 70°C. The transformation temperature ( T _g ) and dilatometric softening temperature ( T _d ) of the SmAS glasses exceeded 800° and 850°C, respectively.     

Thermal Analysis of a SiO2─Al2O3─CaO─CaF2 Glass

A SiO₂─Al₂O₃─CaO─CaF₂ ionomer glass was investigated using thermal analysis, X-ray diffraction, and scanning electron microscopy. The purpose of this investigation was to control the susceptibility of the glass to acid attack. The differential thermal analysis trace exhibited a sharp glass transition at about 645°C and two exotherms. The first exotherm corresponded to liquid–liquid phase separation followed by crystallization of fluorite. The second, much larger, exotherm was the result of crystallization of the remaining glass phase to form anorthite. Prolonged heat treatment below the glass-transition temperature demonstrated that crystallization of fluorite can occur without prior liquid–liquid phase separation.     

Glass-Forming Ability and Crystallization Tendency Evaluated by the DTA Method in the Na2O–B2O3–Al2O3 System

In order to evaluate the crystallization tendency of glasses, the ratio of the crystallization temperature to the liquidus temperature ( T _c/ T _L) was obtained by DTA measurement for the Na₂O–B₂O₃ and Na₂O–B₂O₃–Al₂O₃ systems. The critical cooling rate for glass formation ( Q *) was also measured. The measurements were performed in the composition range of (100 − x )Na₂O–( x )B₂O₃, ( x = 25–35 and 60–100 mol%), and (100 − y )0.5Na₂O·0.5B₂O₃−( y )Al₂O₃, ( y = 6–34 mol%). The relationship between T _c/ T _L and Q * was discussed. A linear relationship between T _c/ T _L and log Q * for these systems was found. Furthermore, the relationship between T _c/ T _L and Q * was verified by computer simulation based on the crystallization kinetics of glass or supercooled liquid.     

Thermopower of YBa2Cu3O7-δ–Ag Composites

The percolation behavior of normal-state thermopower, resistivity, and superconductivity have been studied in YBa₂Cu₃O_7-δ─Ag (YBCO─Ag) composite systems. The normal-state resistivity and thermopower show a percolation threshold at a Ag volume fraction ( V _Ag) of 20% to 30%, whereas the superconducting network shows a threshold at a V _Ag of ≅70% to 80%. The results obtained from this study show that the YBCO─Ag composite obtained from Ag₂O and YBCO powders is uniformly distributed with Ag and YBCO remaining as separate phases without changing their characteristics. The measurements of thermopower indicate that the normal-state thermopower and phonon-drag thermopower are affected by the Ag addition. The stability of YBCO is increased when it is in composite form.     

Subsolidus Phase Relationships in Part of the System Si,Al,Y/N,O: The System Si3N4─AIN─YN─Al2O3─Y2O3

The subsolidus phase relationships in the system Si,Al,Y/N,O were determined. Thirty-nine compatibility tetrahedra were established in the region Si₃N₄─AIN─Al₂O₃─Y₂O₃. The subsolidus phase relationships in the region Si₃N₄─AIN─YN─Y₂O₃ have also been studied. Only one compound, 2YN:Si₃N₄, was confirmed in the binary system Si₃N₄─YN. The solubility limits of the α'─SiAION on the Si₃N₄─YN:3AIN join were determined to range from m = 1.3 to m = 2.4 in the formula Y _{m /3}Si_{12- m} Al _m N₁₆. No quinary compound was found. Seven compatibility tetrahedra were established in the region Si₃N₄─AIN─YN─Y₂O₃.     

Microstructural Evolution in Near-Eutectic Yttrium Silicate Compositions Fabricated from a Bulk Melt and as an Intergranular Phase in Silicon Nitride

Near-eutectic composition Y₂O₃─SiO₂ melts were formed as bulk samples or as an intergranular phase in Si₃N₄. Upon cooling to room temperature the bulk material partially crystallized to γ-Y₂-Si₂O₇ whereas the intergranular phase was glass. On heat-treating at 1500°C the bulk material transformed to γ-Y₂Si₂O₇ whereas the intergranular glass crystallized first to γ-Y₂Si₂O₇ and then to β-Y₂Si₂O₇. Possible reasons for the different behavior are discussed.     

Viscosity of Molten Na2O─B2O3 Slags

The viscosity of sodium borate slags at high Na₂O concentrations (37.3 to 49.4 mol%) and high temperatures (1000° to 1300°C) follows an Arrhenius-type relationship. This relationship was also observed for sodium borate slags (mass% Na₂O/mass% B₂O₃= 0.86) containing CaO and CaF₂ for the same temperature range. There has been a reduction in viscosity of the sodium borate slags (mass% Na₂O₃mass% B₂O = 0.53 to 0.86) with increase in Na₂O concentration. On adding CaO (10 to 50 mass%) to the sodium borate slag (mass% Na₂O/mass% B₂O₃= 0.86), the viscosity increased considerably, while an addition of CaF₂ (S to 15 mass%) to the slag (30.9 mass% Na₂O₃ 35.8 mass% B₂O₃, 33.3 mass% CaO) decreased the viscosity. The average activation energies of Na₂O─B₂O₃, Na₂O─B₂O₃─CaO₃ and Na₂O─B₂O₃─CaO─CaF₂ slag systems have been estimated as 14.6, 124.7, and 41.4 kJ/mol, respectively, for the given composition ranges and 1000° to 1300°C temperature range.     

Neutron Diffraction Study on the Structure of Na-Si-O-N Oxynitride Glasses

The local structure of a Na₂O─SiO₂ oxide glass and a Na₂O─iO₂─Si₃N₄ oxynitride glass has been investigated by the pulsed neutron diffraction method. In the oxide glass, the first peak of radial distribution function (RDF) curves appeared at 0.1627 nm corresponding to Si─O boxh length. In the oxynitride glass, the first peak of the RDF curve was shifted to longer distances at 0.1650 nm due to the coexistence of Si─O and Si─N boxhs. The first peak in the RDF curve of the oxynitride glass was deconvoluted into two peaks whose positions are located at 0.1626 and 0.1709 nm. The one at 0.1626 nm is ascribed to Si─O boxhs and the other at 0.1709 nm to Si─N boxhs. The number of silicon atoms around a nitrogen was found to be 2.42, suggesting that not all of the nitrogen atoms are boxhed to three silicon atoms, but 58% twofold (─N─) and 42% threefold (>N─) nitrogens coexist in the present Na-Si-O-N oxynitride glass. The formation of twofold nitrogens may arise from the reaction between ≡Si─O⁻ and ≡Si₃N groups. This model is compatible with the experimental observation that the density and Vickers hardness of oxynitride glasses increase with the nitrogen content.     

Bioactive Bone Cement Based on CaO─SiO2─P2O5 Glass

A CaO─SiO₂─P₂O₅─CaF₂ glass powder hardened within 4 min when mixed with an ammonium phosphate solution to form CaNH₄PO₄·H₂O. After it had soaked in a simulated body fluid for 3 d, forming hydroxyapatite, the cement showed a compressive strength of 80 MPa. Implanted into a rat tibia, the mixed paste formed a tight chemical bond to the living bone within 4 weeks. Such a bioactive cement could be useful not only for fixing various kinds of implants to the surrounding bones but also, by itself, as a bone filler.     

Ionic Conductivity of the Fluorite-Type Hafnia–R2O3 Solid Solutions

The ionic conductivity of the hafnia-scandia, hafnia-yttria, and hafnia-rare earth solid solutions with high dopant concentrations of 8, 10, and 14 mol% was measured in air at 600° to 1050°C. Impedance spectroscopy was used to obtain lattice conductivity. A majority of the investigated samples exhibited linear Arrhenius plots of the lattice conductivity as a function of temperature. For all investigated dopant concentrations the ionic conductivity was shown to decrease as the dopant radius increased. The activation enthalpy for conduction was found to increase with dopant ionic radius. The fact that the highest ionic conductivity among 14-mol%-doped systems was obtained with HfO₂─Sc₂O₃ suggested that the radius ratio approach should be used to predict the electrical conductivity behavior of HfO₂─R₂O₃ systems. A qualitative model based on the Kilner's lattice parameter map does not seem to apply to these systems. For the three systems HfO₂─Yb₂O₃, HfO₂─Y₂O₃, and Hf₂O₃─Sm₂O₃ a conductivity maximum was observed near the dopant concentration of 10 mol%. Deep vacancy trapping is responsible for the decrease in the ionic conductivity at high dopant concentrations. Formation of microdomains of an ordered compound cannot explain the obtained results. A comparison between the ionic conductivities of doped HfO₂ and ZrO₂ systems indicated that the ionic conductivities of HfO₂ systems are 1.5 to 2.2 times lower than the ionic conductivities of ZrO₂ systems.     

2223 Phase Formation in Bi(Pb)─Sr─C─a─Cu─O: II, The Role of Temperature—Reaction Mechanism

The formation mechanism, the temperature range for the growth, and the thermal stability of the 2223 phase in Bi(Pb)─Sr─Ca─Cu─O have been investigated using DTA/TG, XRD, SEM/EDAX, TEM, EPMA, four-probe resistance and acsusceptibility measurement. The formation of the 2223 phase was found to follow a dissolution–precipitation process. A 2212 phase first reacts with the liquid phase formed via an incongruent melting of the Ca₂PbO₄ phase, and a dissolution of CaO and CuO takes place. The 2201 phase, which has the largest negative free energy, is then precipitated from the melt; the nucleation and growth of the 2223 phase are subsequently developed by the reaction between the 2201 phase precipitates and ions of Ca²⁺ and Cu²⁺ present in the liquid phase. The 2223 phase is formed at temperatures in the range 827°C T < 856°C. The optimum temperature T _f for the formation of 2223 phase is 845°± 5°C. The 2223 phase is thermodynamically unstable at temperatures above 856°C.     

Alkali-Resistant Magnesium Aluminosilicate Oxynitride Glasses

Glasses containing up to 3.3 wt% nitrogen were prepared in the system MgO─Al₂O₃─SiO₂─AIN─Si₃N₄. GlasGlass transition temperature, density, and elastic properties increased with increasing nitrogen content. Resistance against aqueous alkaline solutions was determined by weight loss measurements, solution and surface analysis. The good durability of both oxide and oxynitride glasses is caused by a protective surface layer. The introduction of nitrogen decreases the alkaline attack. The data suggest that nitrogen is incorporated as Si─N boxhs.     

Influence of Thermal History on the Crystallization Behavior and Hardness of a Glass-Ceramic

The glass system SiO₂─Al₂O₃─Li₂O─TiO₂ was examined to determine the dependence of hardness on heat-treatment temperature. In addition to hardness measurements, X-ray diffraction (XRD) was used to determine the type and amount of phases present and to relate this to the hardness results. Hardness increased with heat-treatment temperature. This correlated with the amounts of crystals present, as determined by XRD. For a particular heat-treatment temperature, when hardness was plotted versus load on the indenter, there was a load dependence. There was at first a rapid decrease as the load on the indenter increased, with a constant value being approached at higher loads.     

Formation of Frozen α-Agl in Twin-Roller-Quenched Agl─Ag2 O─MxOy (MxOy= WO3, V2O5) Glasses at Ambient Temperature

Superionic conductor α-AgI, which is stable only above 147°C, was successfully frozen at ambient temperature in AgI─Ag₂O─M_xO_y (M_xO_y= WO₃, V₂O₅) glass matrices by a twin-roller-quenching technique. The system with WO₃, provided the larger composition regions where α-AgI was frozen at ambient temperature, compared to the system with V₂O₅. The matrix glasses with higher glass-transition temperatures had a stronger effect in depressing the α–β transformation of AgI. The α-AgI-frozen samples exhibited extremely large conductivities of 3 × 10⁻²-5 × 10⁻²S.cm⁻¹at 25°C.     

Subsolidus Relations in the La2O3─CuO─CaO Phase Diagram and the La2O3─CuO Binary Join

The phase diagram for the CuO-rich part of the La₂O₃─CuO join was redetermined. La₂Cu₂O₅ was found to have a lower limit of stability at 1002°± 5°C and an incongruent melting temperature of ∼1035°C. LagCu₇O₁₉ had both a lower (1012°± 5°C) and an upper (1027°± 5°C) limit of stability. Subsolidus phase relations were studied in the La₂O₃─CuO─CaO system at 1000°, 1020°, and 1050°C in air. Two ternary phases, La_1.9Ca_1.1Cu₂O_5.9 and LaCa₂Cu₃O_8.6, were stable at these temperatures, with three binary phases, Ca₂CuO₃, CaCu₂O₃, and La₂CuO₄. La₂Cu₂O₅ and La₈Cu₇O₁₉ were stable only at 1020°C, and did not support solid-solution formation.     

Solubility Limits of α'-SiAION Solid Solutions in the System Si,Al,Y/N,O

The solubility limit of α'-SiAION solid solutions on the Si₃N₄─YN:3AIN composition join in the system Si₃N₄─YN─AIN has been determined at 1800°C. The end members of these solid solutions are Y_0.43Si_10.7Al_1.3N₁₆ and Y_0.8Si_9.6Al_2.4N₁₆. Unit-cell dimensions of the α'-SiAION solid solutions in the system Si,Al,Y/N,O can be expressed as follows: a _o(Å) = 7.752 + 0.045 m + 0.009 n , c _o(Å) = 5.620 + 0.048 m + 0.009 n , where the α'-SiAION solid solution has the formula Y _x Si_{12-( m+n )}Al _m+n N_{16- n} O _n . The single-phase boundary of the solid solution α'-SiAION on the composition triangle Si₃N₄─YN:3AIN─AIN:Al₂O₃ is delineated. The present paper also reports the phase relationships involving α'-SiAION.     

Simultaneous Chemical Vapor Deposition of Boron Nitride and Aluminum Nitride

Two chemically different phases, hexagonal BN and AIN, were simultaneously produced by chemical vapor deposition (CVD) using an impinging jet reactor and the BCl₃─AlCl₃─NH₃─Ar reagent system. The microstructure of the BN + AIN composite coatings was strongly dependent on temperature, pressure, and BCl₃ and AlCl₃ concentrations. The growth characteristics of BN and AIN in the codeposition system were similar to those expected from the single-phase deposition processes (i.e., BN-CVD and AIN-CVD), except the growth of AIN whiskers was accentuated, and competition between BN and AIN deposition in the composites was suspected to be the cause of less-crystalline deposits. In both BN + AIN-CVD and AIN-CVD, the growth of AIN whiskers became more apparent with increasing pressure or temperature. The codeposition behavior observed experimentally was compared with thermodynamic predictions.     

An Analysis of Nucleation-Rate Type of Curves in Glass as Determined by Differential Thermal Analysis

The nucleation rate ( I ) versus temperature type of curves for a Na₂O2·CaO·3SiO₂ (NC₂S₃) glass doped with 0.1 wt% platinum, 0.5 wt% Ag₂O, and 2.0 wt% P₂O₅ were determined using a previously developed differential thermal analysis (DTA) technique. In this DTA technique, a constant amount of glass sample was nucleated at selected temperatures for a specific time, followed by a DTA scan at a fixed heating rate. The functional dependence of the maximum intensity of the exothermic DTA crystallization peak ((delta T )_p) or the inverse temperature at the DTA peak maximum ( T _p⁻¹) on the nucleation temperature ( T _n) was used to determine the nucleation rate versus temperature type of curves. Calculations for qualitatively assessing the dependence of (delta T )_p on T _n were performed using I and crystal growth rate ( U ) curves for a hypothetical system. Values of (delta T )_p calculated for different degrees of overlap between the I and U curves were compared with those measured experimentally. The (delta T )_p vs T _n curves depended strongly on the overlap of I and U , whereas the T _p⁻¹ vs T _n curves were unaffected by the overlap.     

X-ray Absorption Studies of Ceria with Trivalent Dopants

The local structural environments of Sc³⁺ and Gd³⁺ in ceria were studied for the first time by using EXAFS (extended X-ray absorption fine structure) and XANES (X-ray absorption near edge structure) spectroscopy. Our results indicate that Sc³⁺ in 10-mol%-Sc₂O₃-doped ceria has a 7-fold-coordinated Sc-ordered structure with two different Sc─O distances (2.13 and 2.26 Å). An octahedrally coordinated Sc─O cluster is present in 5 mol% Sc₂O₃─5 mol% Gd₂O₃─CeO₂, because of the strong scavenging effect of Sc³⁺ ions on oxygen vacancies created by Gd³⁺. The Gd³⁺ in this sample is largely unassociated. Sc₂O₃ (5 mol%) and Gd₂O₃ (5 or 10 mol%) form random solid solutions with CeO₂. These results are consistent with the current concept of defect structures in this structural family.