Effect of TiO2 addition on oxidation behavior of sintered bodies composed of Si3N4-Y2O3-Al2O3-AlN

The effect of TiO₂ content on the oxidation of sintered bodies from the conventional Si₃N₄-Y₂O₃-Al₂O₃-AlN system was investigated. Sintered specimens composed of Si₃N₄, Y₂O₃, Al₂O₃, and AlN, with a ratio of 100 : 5 : 3 : 3 wt% and containing TiO₂ in the range of 0 to 5 wt% to Si₃N₄, were fabricated at 1775 °C for 4 h at 0.5 MPa of N₂. Oxidation at 1200 to 1400 °C for a maximum of 100 h was performed in atmospheres of dry and wet air flows. The relation between weight gain and oxidation time was confirmed to obey the parabolic law. The activation energies decreased with TiO₂ content. In the phases present in the specimens oxidized at 1300 °C for 100 h in dry air, Y₃Al₅O₁₂ and TiN, which had existed before oxidation, disappeared. Alpha-cristobalite and Y₂O₃·2TiO₂ (Y2T) appeared in their place and increased with increasing TiO₂ content. In those oxidized at 1400 °C, -cristobalite was dominant and very small amounts of Y₂O₃·2SiO₂ and Y2T were contained. There was a tendency for more -cristobalite to form in oxidation in wet air than in dry air. Therefore, moisture was confirmed to affect the crystallization of SiO₂ formed during oxidation. Judging from the lower activation energy, the crystallization, and the pores formation, we concluded that the addition of TiO₂ decreases oxidation resistance.     

Polymorphism of the Ag8S4O4 and Ag6S3O4 compounds

Experimental results of the reaction occurring between aqueous solutions of AgNO₃ and Na₂S₂O₃ were presented in this work. It has been demonstrated that these reagents form two phases to which the summary formulas: -Ag₈S₄O₄ and -Ag₆S₃O₄ were ascribed. The -Ag₈S₄O₄ phase crystallizes in a tetragonal system and has the following parameters of the unit cell: a = b = 0.72052 nm, c = 0.51140 nm, V = 0.26550 nm³, Z = 1, d_x = 6.60 g/cm³. At 223°C -Ag₈S₄O₄ undergoes an irreversible, endothermic polymorphic transition. The heat of this transition amounts 8.03 × 10^–3 J/mol. A high-temperature polymorphic form -Ag₈S₄O₄ melts at 400°C. The -Ag₆S₃O₄ phase crystallizes in a monoclinic system and has the following parameters of the unit cell:a = 2.09616 nm, b = 0.53118 nm, c = 1.49885 nm, = 102.78°, V = 1.62753 nm³, Z = 8, d_x = 6.59 g/cm³. -Ag₆S₃O₄ also undergoes an irreversible, endothermic polymorphic transition at 221°C. The heat of this transition amounts 7.65 × 10^–3 J/mol. A high-temperature form, -Ag₆S₃O₄, melts at 390°C.     

Non-ohmic behaviour of the binary ZnO-Nb2O5 system

Studies have been made of the non-ohmic behaviour of the system ZnO-Nb₂O₅, as a function of composition, in the range 0.1 to 0.5 wt % of Nb₂O₅ and sintering temperature varying from 900 to 1300° C. It is found that the non-linearity coefficient varies with composition and sintering temperature. The maximum value of ( 8) is achieved for the samples containing 0.2 wt% Nb₂O₅, sintered at 1100°C. These results are interpreted in terms of the variation of barrier height with composition.     

Analytical electron microscopy of Al2O3 implanted with iron ions

Single crystals of -Al₂O₃ were implanted with iron ions at room temperature to fluences ranging from 4×10¹⁶ Fe cm^–2 to 1×10¹⁷ Fe cm^–2. The microstructure and composition in the implanted region were examined using analytical electron microscopy techniques. Special emphasis was placed on monitoring the microstructural changes which take place during post-implantation annealing. Clusters of metallic -Fe were identified in the specimen after implantation to a dose of 1×10¹⁷ Fe cm^–2. Analytical electron microscopy of implanted specimens annealed in oxygen revealed the redistribution of the implanted iron and the formation of surface precipitates of -Fe₂O₃, subsurface precipitates of various forms of spinel, and, in some cases, subsurface precipitates of iron, depending on the annealing temperature. Examination of implanted specimens annealed under reducing conditions revealed the presence of precipitates of -Fe.     

Pressureless sintering of Y2O3-CeO2-doped sialons

Various sialon materials have been prepared by pressureless sintering at 1775 and 1825 °C using Y₂O₃ and/or Ce0₂ as sintering aids. Constant molar amounts of the oxide mixtures were added in the ratios Y₂O₃/CeO₂: 100/0, 75/25, 50/50, 25/75, 0/100 corresponding to 6.0 and 9.25 wt% for the pure Y₂O₃ and pure CeO₂, respectively. Only one of the compositional series reached full density at 1775 °C with cerium replacing yttrium, whereas at 1825 °C all compositional series except one became dense. The samples sintered showed that yttrium but not cerium stabilizes the sialon phase in these ceramics. The dense cerium-sialon ceramics sintered at 1825 °C have as good hardness and indentation fracture toughness as the corresponding yttrium-sialon ceramics, or even higher for the sialon type of materials. For the mixed - sialon materials the hardness decreased as the amount of a sialon phase decreased by increasing cerium-doping.     

Effects of Y<Subscript>2</Subscript>O<Subscript>3</Subscript> on the microstructure and electrical properties of Pr-ZnO varistors

Effects of Y₂O₃ contents on the microstructure and electrical properties of Pr₆O₁₁-based ZnO varistor have been studied. The varistor voltage (V_1mA) and the nonlinear exponent () increased with increasing Y₂O₃ contents, whereas the dielectric constant decreased. Y-rich phase segregated at nodal points in grain boundaries. The average grain size decreased with increasing Y₂O₃ content. The specimen with 4.0 mol% Y₂O₃ sintered at 1285 C exhibited the highest nonlinear exponent ( = 77) with the dielectric constant, ~352 at 1 kHz.     

Hot isostatic pressing of tetragonal ZrO2 solid-solution powders prepared from acetylacetonates in the system ZrO2-Y2O3-Al2O3

In compositions having ZrO₂/Y₂O₃=(74.25–71.25)/(0.75–3.75) (mol% ratio) with 25 mol% Al₂O₃, metastable t-ZrO₂ solid solutions crystallize at 780° to 860°C from amorphous materials prepared by the simultaneous hydrolysis of zirconium, yttrium and aluminium acetylacetonates. Hot isostatic pressing has been performed for 1 h at 1130 and 1230°C under 196 MPa using their powders. Two kinds of material are fabricated: (i) perfect ZrO₂ solid-solution ceramics and (ii) composites of ZrO₂ solid solution and -Al₂O₃. Their mechanical properties are examined, in connection with microstructures and t/m ZrO₂ ratios. Composites with a homogeneous dispersed -Al₂O₃ derived from solid-solution ceramics result in a remarkable increase of strength.     

Formation of iron oxides by the oxidation of iron in Fe-MOH-H2O and Fe-MOH-H2O-O2 systems (M = Li,Na, K)

The oxidation behaviours of iron powders, ca. 100 m in diameter, in 5–50 m NaOH, 5–40 m KOH and 5–40 m LiOH solutions at 373–573 K were investigated in the absence and presence of oxygen, where m is molality. The oxidation of iron proceeded noticeably above 423 K to form Fe₃O₄, -Fe₂O₃, -NaFeO₂, -Fe₂O₃, Li _x Fe_3–xO₄ and -LiFeO₂ depending on the reaction conditions. The rate of oxidation in LiOH solutions was much slowerthan those in NaOH and KOH solutions.     

Effect of CeO2, MgO and Y2O3 additions on the sinterability of a milled Si3N3 with 14.5 wt% SiO2

Specimens of milled -Si₃N₄ with 0 to 5.07 equivalent per cent of CeO₂, MgO or Y₂O₃ additions were pressureless sintered at 1650 to 1820° C for 4 h in static nitrogen at 34.5 kPa (5 psi) gauge pressure and while covered with a mixture of Si₃N₄+SiO₂ powders. The density — per cent addition — temperature plots showed maxima which, for all three additives, occurred between 1.2 and 2.5 equivalent per cent. Maximum densities resulted on sintering in the 1765 to 1820° C range and were 99.6 per cent of theoretical with 2.5 equivalent per cent CeO₂, 98.5 per cent of theoretical with 1.24 to 1.87 equivalent per cent MgO, and 99.2 per cent of theoretical with 2.5 equivalent per cent Y₂O₃. Also, densities 94 per cent of theoretical were obtained with as little as 0.62 equivalent per cent additive (1.0 MgO, 2.11 CeO₂ or 1.85 Y₂O₃, in wt%). X-ray diffraction showed that the materials were predominantly -Si₃N₄ with some or no Si₂N₂O. Scanning electron photomicrographs showed microstructures of elongated grains with aspect ratios of about 5, with all additives.     

EPR study of Cu2+ in Na2O-NaF-B2O3-Bi2O3 glasses

Electron paramagnetic resonance (EPR) studies have been performed on the glass system (30–x) NaF-xNa₂O-50B₂O₃-20Bi₂O₃ doped with CuO as a paramagnetic probe. The calculated g values indicate that Cu²⁺ is in a tetragonally elongated octahedral co-ordination, and the Jahn-Teller character gives rise to anisotropic hyperfine structure. The spin-Hamiltonian parameters and -bonding parameter, ², are calculated. Varying the fluoride ion concentration and its effect on these parameters is also discussed.     

Si3N4-ZrO2 composites with small Al2O3 and Y2O3 additions prepared by HIP

Si₃N₄-ZrO₂ composites have been prepared by hot isostatic pressing at 1550 and 1750 °C, using both unstabilized ZrO₂ and ZrO₂ stabilized with 3 mol% Y₂O₃. The composites were formed with a zirconia addition of 0, 5, 10, 15 and 20 wt%, with respect to the silicon nitride, together with 0–4 wt% Al₂O₃ and 0–6 wt% Y₂O₃. Composites prepared at 1550 °C contained substantial amounts of unreacted -Si₃N₄, and full density was achieved only when 1 wt% Al₂O₃ or 4 wt % Y₂O₃ had been added. These materials were generally harder and more brittle than those densified at the higher temperature. When the ZrO₂ starting powder was stabilized by Y₂O₃, fully dense Si₃N₄-ZrO₂ composites could be prepared at 1750 °C even without other oxide additives. Densification at 1750 °C resulted in the highest fracture toughness values. Several groups of materials densified at 1750 °C showed a good combination of Vickers hardness (HV10) and indentation fracture toughness; around 1450 kg mm^–2 and 4.5 MPam^1/2, respectively. Examples of such materials were either Si₃N₄ formed with an addition of 2–6 wt% Y₂O₃ or Si₃N₄-ZrO₂ composites with a simultaneous addition of 2–6 wt%Y₂O₃ and 2–4 wt% Al₂O₃.     

Surface nucleation and cellular growth kinetics of cordierite glass ceramics containing 3 mol % Y2O3-ZrO2

Cordierite-based glass ceramics of the 2MgO2Al₂O₃5SiO₂ composition with t-ZrO₂ (3 mol% Y₂O₃-ZrO₂) and P₂O₅ addition, was heat-treated isothermally and isochronically for crystallization studies. Major crystalline phases incurred by the heat treatment were t-ZrO₂ and -cordierite. Surface nucleation predominated when edge and corner nucleation in these samples were suppressed regardless of their radii of curvature. Crystallization began with the formation of -quartz S.S. and its transformation to -cordierite was followed by prolonged heating. Cellular growth of -cordierite on the surface of the quenched glass plates, gave a linear kinetics. The activation energy for cellular growth was 410 kJ mol^–1.     

Phase Composition of the Products of Fe Oxidation in Fe + C + NaCl + H2O + O2 Exothermic Mixtures

Using thermodynamic analysis of the Fe–C–NaCl–H₂O–O₂ system and experimental studies (x-ray diffraction and Mössbauer spectroscopy) of exothermic mixtures containing Fe metal, activated carbon, water, and NaCl, we identified the state of Fe and determined the phase composition of the reaction products at different stages of oxidation with atmospheric oxygen. The calculation and experimental results are in reasonable agreement. Under the conditions of restricted access for air, the main oxidation product is magnetite, Fe₃O₄. Free access for air leads to the formation of hydrous ferric oxide, Fe₂O₃ · nH₂O. The most stable phase under the conditions of interest is goethite, Fe₂O₃ · H₂O (-FeOOH). Storage of incompletely oxidized samples away from air for 7–14 days leads to partial reduction of iron(III) oxide phases to Fe₃O₄ and -Fe.     

Formation of oxide phases in the system Fe2O3-NiO

Mixed metal oxides in the system Fe₂O₃-NiO were prepared by coprecipitation of Fe(OH)₃/Ni(OH)₂ and the thermal treatment of hydroxide coprecipitates up to 800 or 1100°C. X-ray diffraction showed the presence of -Fe₂O₃, NiO and NiFe₂O₄ in samples prepared at 800°C. The oxide phases -Fe₂O₃, NiO, NiFe₂O₄ and a phase with structure similar to NiFe₂O₄ were found in samples prepared at 1100°C. Fourier transform-infrared spectra of oxide phases formed in the system Fe₂O₃-NiO are discussed. Two very strong infrared bands at 553 and 475 cm^–1, a weak intensity infrared band at 383 cm^–1 and two shoulders at 626 and 441 cm^–1 were observed for -Fe₂O₃ prepared at 1100°C. NiFe₂O₄, prepared at the same temperature, showed two broad and very strong infrared bands at 602 and 411 cm^–1, while NiO showed a broad infrared band at 466 cm^–1. Fourier transform infrared spectroscopic results were in agreement with X-ray diffraction.     

The effect of additives on the crystallization and sintering of 2MgO-2Al2O3-5SiO2 glass-ceramics

Crystallization and sintering behaviour of three cordierite (2MgO-2Al₂O₃-5SiO₂) glasses containing different amount of additives were investigated and compared by using differential thermal analysis (DTA), X-ray diffraction (XRD), scanning electron microscopy (SEM), and the Archimedes method. The stoichiometric 2MgO-2Al₂O₃-5SiO₂ (MAS) glass and the 2MgO-2Al₂O₃-5SiO₂ glass containing 3 wt% of B₂O₃ and 3 wt% of P₂O₅ (MASBP) showed two exotherms (one for -cordierite formation from a glass and the other for -cordierite formation from the -cordierite phase), whereas the 2MgO-2Al₂O₃-5SiO₂ glass containing 2 wt % of B₂O₃, 2 wt% of P₂O₅, and 2 wt % of TiO₂ (MASBPT) showed only a single exotherm representing -cordierite formation. By using Kissinger, Augis-Bennett, Ozawa, and modified Kissinger methods, the activation energy values for -cordierite formation in the MASBP and MASBPT glasses were determined as 310±6 and 326±13 kJ mol^–1, respectively, whereas that in the MAS glass was determined as 868±5 kJ mol^–1. The MASBPT glass showed the lowest peak temperature value for -cordierite formation (980 °C) amongst the three glasses. Both the MASBP and MASBPT glasses showed excellent sintering behaviour (> 99.7% of theoretical density).     

Hot isostatic pressing of Si3N4 with Y2O3 additions

The effect of Y₂O₃ additive on the properties of hot isostatically pressed silicon nitride was studied. The influence of small additions of Y₂O₃ on the densification of silicon nitride was investigated. The density and elastic moduli of the product increase with increasing of the Y₂O₃ additions. The hot isostatically pressed pure silicon nitride consists of -Si₃N₄, -Si₃N₄and Si₂N₂O; phase content of the hot isostatically pressed silicon nitride with 10 wt % Y₂O₃addition consists of -Si₃N₄, yttrium silicate and Y₂Si₃O₃N₄. The effect of the outgassing of the specimens prior to hot isostatical pressing on the properties of the final material is discussed.     

Sintering process of Y2O3 and Al2O3-doped Si3N4

The sintering process of Y₂O₃- and Al₂O₃-doped Si₃N₄ has been investigated by dilatometry and microstructural observations. The densification progressed through three processes. The bulk density increased to 85% theoretical without the formation of -Si₃N₄ in the initial process. The densification once terminated after the second process. The / transformation of Si₃N₄ and the related formation of prismatic grains reduced the densification rate in the second process, although the grain size and the aspect ratio were very small. The final process was the densification of -Si₃N₄, where the fibrous grains grew remarkably. The kinetic order for the densification of -Si₃N₄ indicated a diffusion-rate controlling mechanism with the activation energy of 244 kJ mol^–1 (<1450 ° C) and 193 kJ mol^–1 (>1450 ° C). The influence of heating rate on the grain growth was characterized by a parameter derived from kinetic parameters. The relationships between grain growth and densification behaviour have also been discussed.     

High temperature oxidation behavior of Ti-Al-Nb ternary alloys

The oxidation behavior of four Ti-Al-Nb ternary alloys with different microstructures were investigated at 1000°C using interrupted oxidation test in air. Alloys with single-phase -TiAl, two-phase -TiAl + ₂-Ti₃Al, multi-phase -TiAl + ₂-Ti₃Al + Nb₂Al and two-phase ₂-Ti₃Al + Nb₂Al were prepared. The oxidation resistance of the Ti-Al-Nb ternary alloy at high temperature was found to be better than that of the binary Ti-Al alloy. Among the four Ti-Al-Nb ternary alloys, the + ₂ two-phase alloy has the best oxidation resistance. The presence of Nb-enriched phase such as Nb₂Al and Nb₃Al decrease the oxidation resistance at elevated temperature presumably due to the formation of Nb₂O₅, which would accelerate the exfoliation of oxide.     

Microstructural development and mechanical properties of pressureless-sintered SiC with plate-like grains using Al2O3-Y2O3 additives

Dense SiC ceramics with plate-like grains were obtained by pressureless sintering using -SiC powder with the addition of 6 wt% Al₂O₃ and 4 wt% Y₂O₃. The relationships between sintering conditions, microstructural development, and mechanical properties for the obtained ceramics were established. During sintering of the -SiC powder compact the equiaxed grain structure gradually changed into the plate-like grain structure that is closely entangled and linked together through the grain growth associated with the phase transformation. With increasing holding time, the fraction of phase transformation, the grain size, and the aspect ratio of grains, increased. Fracture toughness increased from 4.5 MPa m^1/2 to 8.3 MPa m^1/2 with increasing size and aspect ratio of the grains. Crack deflection and crack bridging were considered to be the main operative mechanisms that led to improved fracture toughness.     

Microhardness and microbrittleness of several crystalline glass ceramic phases

The micromechanical properties of crystals of -cordierite, spinel, rutile, mullite, -cristobalite, and magnesium aluminosilicate have been studied. It was shown that the maximum Vickers hardness and maximum Dertev microbrittleness are found for crystals of magnesium aluminosilicate, cordierite, and spinel. The minimum values of these parameters are found for crystals of -cristobalite.Translated from Problemy Prochnosti, No. 10, pp. 29–31, October, 1992.