Alumina as a Devitrification Inhibitor during Sintering of Borosilicate Glass Powders

Cristobalite is formed when borosilicate glass (Corning Code 7740) is sintered at temperatures ranging from 700^o to 1000^o C. The precipitation kinetics, determined by XRD analysis, exhibit a characteristic incubation period which decreases with increasing sintering temperature, from 60-120 min at 700^oC to 3-5 min at 1000^o C. Activation analysis of precipitation shows an activation energy of 75 kJ/mol, which is close to that for the diffusion of Na+ in borosilicate glass, suggesting mass-transport controlled kinetecs. ^1.,5With added alumina content greater than a critical value, however, the cristobalite formation in the borosilicate glass is completely prevented at the sintering temperatures investigated. The critical alumina content is found to decrease with decreasing alumina particle size but with increasing sintering temperature. The above result, similar to observations previously made in a binary glass mixture containing a low-softening borosilicate glass (BSG) and a high-softening high silica glass (HSG) ³ is attributed to a strong coupling between Al³⁺ from alumina and Na⁺ from borosilicate glass. The coupling reaction causes segregation of Na⁺ in boraosilicate glass to alumina, thus forming a Na⁺-and Al³⁺-rich reaction layer around alumina particles far too rapid for cristobalite formation.     

Strengthening of Porous Alumina by Pulse Electric Current Sintering and Nanocomposite Processing

Porous Al₂O₃ and SiC–dispersed-Al₂O₃ (Al₂O₃/SiC) nanocomposites with improved mechanical properties were fabricated using pulse electric current sintering (PECS). Microstructures with fine grains and enhanced neck growth, as well as high fracture strength, could be achieved via PECS of Al₂O₃. The incorporation of fine SiC particles into an Al₂O₃ matrix significantly increased the fracture strength of porous Al₂O₃. Based on microstructural observations, it was revealed that the refinement of Al₂O₃ grains and neck growth occurred by PECS and nanocomposite processing.     

Pulse Electric Current Sintering of Al2O3/3 vol% ZrO2 with Constrained Grains and High Strength

The pulse electric current sintering technique (PECS) was demonstrated to be effective in rapid densification of fine-grained Al₂O₃/3Y-ZrO₂ using available commercial powders. The composites attained full densification (>99% of TD) at 1450°C in less than 5 min. The composites sintered at a high heating rate had a fine microstructure. The incorporation of 3 vol% 3Y-ZrO₂ substantially increased the average fracture strength and the toughness of alumina to as high as 827 MPa and 6.1 MPa·m^1/2, respectively. A variation in the heating rate during the PECS process influenced grain size, microstructure, and strength, though there was little or no variation in the fracture toughness.     

Homogeneous Distribution of Sintering Additives in Liquid-Phase Sintered Silicon Carbide

The addition of sintering additives to silicon carbide particles by electrostatic adsorption of colloidal A1₂O₃ and Y₂O₃ sols has been studied as a way to achieve an optimum homogeneity in the microstructure. The adsorption behavior of the sol particles was examined by electrophoretic measurements and X-ray fluorescence analysis. Both A1₂O₃ and Y₂O₃ sols could simultaneously be adsorbed on the SiC particle surfaces. Viscosity measurements showed that the colloidal sol particles had a stabilizing effect on the slip, and hence slips with relatively high solid loadings could be prepared without adding extra dispersing agent. Liquid-phase-sintered silicon carbide materials (LPS-SiC) with 2 wt% A1₂O₃ and 1 wt% Y₂O₃ were prepared by freeze granulation/ pressing and sintering at 1880^deg;C for 4 h. The homogeneity of the green compacts was quantified using a spot analysis technique in an electron probe microanalyzer. It was clearly shown that the addition of sols gave a more homogeneous microstructure than the reference sample with Y₂O₃ and A1₂O₃ added as powders. The addition of sintering additives as sols also enhanced the sintering behavior.     

Characterization of Thermoelectric Metal Oxide Elements Prepared by the Pulse Electric-Current Sintering Method

Thermoelectric elements consisting of the layered polycrystalline materials of Al-doped ZnO and NaCo₂O₄ were prepared using the pulse electric-current sintering (PECS) method at 900°C for 3 min. Direct contact between the polycrystalline Al-doped ZnO and the NaCo₂O₄ was obtained in a single-step process for the stacked powders. The electrical conductivities of the polycrystalline materials prepared by PECS were higher than those of materials prepared by conventional sintering, despite their porous structure. The thermoelectric voltage of the 1-mol%-Al-doped ZnO and NaCo₂O₄ polycrystalline element (measuring ∼6 mm × 3 mm × 15 mm) was 83 mV at d T = 500 K, when the junction of the elements was at 800°C.     

Chemical Characterization of Si-Al-C-O Precursor and Its Pyrolysis

Polycarbosilane was modified by reaction with an aluminum alkoxide to get a precursor for Si-Al-C-O ceramics. The precursor was essentially characterized by magic-angle spinning nuclear magnetic resonance (²⁹Si, ²⁷Al, and ¹³C) and appeared as a dispersion of Al(OH)₃-based particles in a polycarbosilane chain matrix. After the material was heat-treated under argon at 1500°C, X-ray diffraction showed that it crystallized mainly as SiC 2H. The presence of this rather unusual polytype for polycarbosilane-derived ceramics seemed to be related to the presence of aluminum atoms.     

Effect of Silicon Dioxide on the Thermal Diffusivity of Aluminum Nitride Ceramics

The thermal diffusivity of AlN ceramics was significantly decreased by the addition of SiO₂. The AlN ceramics with 4 wt% SiO₂ could not be densified by pressureless sintering in the temperature range 1400° to 1800°C. The thermal diffusivity of these samples was very low because of their porous structure. The AlN ceramics containing 2, 4, and 8 wt% SiO₂ were densified by hot-pressing and also had low thermal diffusivity. In these samples, the grains of the 27R polytype that resulted from the reaction between AlN and SiO₂ were dispersed, obstructing the conduction of heat. The relation between the amount of 27R polytype and the thermal diffusivity of the AlN ceramics was determined.     

Enhanced Formation of Calcia-Gallia Glass by Containerless Processing

Glass formation from melts of 44 CaO 56Ga₂O₃(mol%) was investigated under containerless conditions obtained by acoustically stabilized aerodynamic levitation in combination with laser beam heating. The critical cooling rate for glass formation was R_c <100°C/s, much less than values reported in the literature ( R_c =550^o±120^o C/s and ca 350^oC/s) for pendant drops of this composition attached to Pt-Rh thermocouples. High values of R_c in pendant drop experiments were confirmed for the specimens used in this work.     

Influence of Copper(II) Oxide Additions to Zinc Niobate Microwave Ceramics on Sintering Temperature and Dielectric Properties

The effect of CuO additions on the firing temperature of ZnNb₂O₆ ceramics was investigated using dilatometry, transmission electron microscopy, and X-ray diffractometry. A 5 wt% CuO addition to ZnNb₂O₆ ceramics significantly lowered the firing temperature from 1150° to ∼900°C. The presence of a CuO-rich intergranular phase in the specimen was observed and was evidence of the formation of a liquid phase during sintering. The composition of the liquid phase was (ZnCu₂)Nb₂O₈. In particular, the low-fired ZnNb₂O₆ ceramics had good microwave dielectric characteristics— Q × f = 59 500, ɛ_r= 22.1, τ_f=–66 ppm/^oC. These properties were correlated with the formation of a second phase, (ZnCu₂)Nb₂O₈.     

Effects of Additives on the Pressure-Assisted Densification and Properties of Silicon Carbide

The densification of silicon carbide (SiC) was studied using a variety of additives (Al, AlN, Al₂O₃, B₄C, C, Si₃N₄, and Y₂O₃). The onset of densification of SiC with small amounts of additives occurred at temperatures between 1500° and 1900°C with 28 MPa applied pressure. Al, B₄C, and C promoted densification, while N (added as AlN or Si₃N₄) retarded sintering. A 96.75 wt% SiC–2 wt% Al–1 wt% C–0.25 wt% B₄C starting composition yielded the same percent of theoretical density (in the range of 70%–90% theoretical density) 400°C lower than a 95 wt% SiC–5 wt% AlN material. Yttria additions promoted intergranular fracture, which increased the single-edged precracked beam fracture toughness. The appropriate selection and amount of additives allowed for the tailoring of grain size and intergranular fracture, thus controlling the mechanical properties. While oxygen was present in all materials containing aluminum, the incorporation of additional oxygen as alumina resulted in reduced sintering activity compared with Al metal. Corrosion resistance decreased in both HF and NaOH solutions at 80°C for materials containing a grain boundary phase.     

Silicon Nitride/Silicon Carbide Nanocomposite Materials: I, Fabrication and Mechanical Properties at Room Temperature

The fabrication of dense Si₃N₄/SiC nanocomposite materials that contained 2.5-30 wt% SiC via gas-pressure sintering and hot pressing was investigated. The SiC particles originated from admixed commercial SiC powders, SiCN powders produced by plasma synthesis, in situ reaction pyrolysis of carbon-coated Si₃N₄ particles, and pyrolysis of a polycarbosilazane-based SiCN precursor. Based on thermodynamic calculations, criteria for minimum liquid-phase decomposition during sintering were developed. The best sintering results were obtained for sintering cycles that observed this criteria. Materials that contained plasma-synthesized SiCN exhibited high strengths (835-995 MPa) and fracture toughness values (7.4-7.8 MPam^1/2) at room temperature. Post-sintering thermal treatments led to a strength reduction.     

Effect of Weight Loss on Liquid-Phase-Sintered Silicon Carbide

The evaporation of silicon carbide (SiC) ceramics during sintering has been studied by thermogravimetry in a graphite furnace filled with argon. The SiC powder compacts contained 7.5 wt% eutectic composition of Y₂O₃–Al₂O₃ to promote liquid-phase sintering. A weight loss of 1–11 wt% was observed during sintering, depending on the sintering temperature and sintering time. The weight loss severely influenced the final density and the microstructure of the SiC ceramics. Particularly, the oxide sintering aids, which were homogeneously distributed in the green ceramics, were observed to segregate and form particular patterns that were dependent on the temperature, sintering time, and the total weight loss. Possible heterogeneous reactions evolving volatile species have been discussed in relation to the experimental observations.     

Differential Sintering by Improper Selection of Sintering Parameters during Pulse Electric Current Sintering

Recently, we reported on the retention of fine-grained micro-structure in Al₂O₃/3 vol% 3Y-ZrO₂ composites using the pulse electric current sintering (PECS) technique. It was demonstrated that a high heating rate is beneficial for the retention of fine grains and homogeneous microstructure. As there are few reports on microstructural inhomogeneity and excessive grain growth in compacts densified by the PECS technique, we carried out a series of experiments on monolithic alumina by varying the sintering parameters and discussed the characteristic results. All specimens that were densified under selective sintering conditions attained high density (∼99% of the theoretical density) at 1250°3C in > 5 min. The average fracture strength of monolithic alumina was observed to be 741 ± 25 MPa and the fracture toughness was 2.2 MPa.m <^1/2, and these were reasoned out to small grains. However, compacts sintered under very low compaction pressure attained ∼92%-93% of the theoretical density, and these specimens had undesirable microstructural inhomogeneity owing to differential sintering. Hence, in the present study, we address the problem of differential sintering.     

Mössbauer Study of the Influence of Fe-Si-N Liquid in the Synthesis of β-Si3N4 from Silica

Mössbauer spectra of the products obtained by carbothermal reduction and distribution of silica in the presence of iron in the temperatures range 1200^o to 1540^o were studied. The preponderance of β- Si₃N₄ over the α form at a higher reaction temperature were assumed to be related to the formation of an Fe-Si-N liquid. The liquid did not alter its composition with the variation of reduction-temprature, Iron had no effect on the reaction mechanism below 1300^oC.     

Effect of SiC on Interfacial Reaction and Sintering Mechanism of TiB2

Compacts of TiB₂ with densities approaching 100% are difficult to obtain using pressureless sintering. The addition of SiC was very effective in improving the sinterability of TiB₂. The oxygen content of the raw TiB₂ powder used in this research was 1.5 wt%. X-ray photoelectron spectroscopy showed that the powder surface consisted mainly of TiO₂ and B₂O₃. Using vacuum sintering at 1700°C under 13–0.013 Pa, TiB₂ samples containing 2.5 wt% SiC achieved 96% of their theoretical density, and a density of 99% was achieved by HIPing. TEM observations revealed that SiC reacts to form an amorphous phase. TEM-EELS analysis indicated that the amorphous phase includes Si, O, and Ti, and X-ray diffraction showed the reaction to be TiO₂+ SiC → SiO₂+ TiC. Therefore, the improved sinterability of TiB₂ resulted from the SiO₂ liquid phase that was formed during sintering when the raw TiB₂ powder had 1.5 wt% oxygen.     

Pressureless Sintering of Dense Si3N4 and Si3N4/SiC Composites with Nitrate Additives

The effect of aluminum and yttrium nitrate additives on the densification of monolithic Si₃N₄ and a Si₃N₄/SiC composite by pressureless sintering was compared with that of oxide additives. The surfaces of Si₃N₄ particles milled with aluminum and yttrium nitrates, which were added as methanol solutions, were coated with a different layer containing Al and Y from that of Si₃N₄ particles milled with oxide additives. Monolithic Si₃N₄ could be sintered to 94% of theoretical density (TD) at 1500°C with nitrate additives. The sintering temperature was about 100°C lower than the case with oxide additives. After pressureless sintering at 1750°C for 2 h in N₂, the bulk density of a Si₃N₄/20 wt% SiC composite reached 95% TD with nitrate additives.     

Preparation and Analysis of a Silicon Carbide Composite Membrane

Silicon carbide (SiC) porous substrates, containing alumina (Al₂O₃) dopant levels of 3, 5, and 8 wt%, are prepared by slip casting and sintering in the temperature range of 1450°–1800°C. The linear shrinkage, bulk density, and pore size of the sintered substrate increase as the sintering temperature and the amount of dopant increase. A large amount of β-phase SiC is transformed to α-phase SiC if the dopant concentration is 5 or 8 wt%. The flexural strength of the substrate doped with 8 wt% Al₂O₃ is higher than that of the substrate doped with 3 wt% Al₂O₃; however, the Weibull modulus of the former is lower. SiC composite membranes of improved selectivity and strength are fabricated by coating the porous substrate with layers of lower Al₂O₃ contents at lower sintering temperatures.     

Effects of Additives on Microstructure and Properties of Alumina-Silicon Carbide Nanocomposites

Al₂O₃/5-vol%-SiC nanocomposites have been fabricated by using pressureless sintering with MgO and/or Y₂O₃ sintering aids and post-hot isostatic pressing (HIPing), which circumvents the limitations of hot pressing. Al₂O₃/SiC nanocomposites that have been doped with 0.1 wt% MgO and 0.1 wt% MgO + 0.1 wt% Y₂O₃ show an increased sintering density and a homogeneous microstructure, as well as a high fracture strength (1 GPa) after HIPing. In contrast, using Y₂O₃ as a dopant has a negative impact on the microstructure and the fracture strength. The results suggest that MgO, as a sintering additive, has a key role in improving the densification and controlling the microstructure of Al₂O₃/SiC nanocomposites.     

Crystallization and Properties of a Si-Y-Al-O-N Glass-Ceramic

Glasses have been prepared in the Si -Y-Al O-N system by melting mixtures of silica, alumina, yttria, and silicon nitride. One particular glass containing 17 equiv% N has been investigated to Observe the crystallization at temperatures in the range 1050^o-1300^oC. The major crystalline phase observed is Y₂Si₂O₇, existing as the α form below 1200^oC and the β form above this temperature. Properties of the glass-ceramic, including thermal expansion coefficient, hardness, electrical resistivity, and creep have been assessed.     

Dispersion of SiC in Aqueous Media with Al2O3 and Y2O3 as Sintering Additives

It has been well accepted that polyethylene imine (PEI) is an effective dispersant for silicon carbide (SiC) in aqueous media. However, after the addition of sintering additives (Al₂O₃ and Y₂O₃), this dispersing effect is reduced significantly. In this work, a second dispersant, citric acid, was used to resolve this problem. It was found that citric acid could decrease the slurry viscosity (without sintering additives) and enhance the PEI adsorption on SiC particle surface. The optimal amount of citric acid required to achieve a minimum viscosity for 55 vol% SiC suspensions was equal to ∼0.87 wt% (at pH ∼6.8). With the aid of citric acid, well-stabilized SiC suspensions (containing sintering additives) were realized, which exhibited slight shear thinning rheologies. After tape casting and SPS sintering, dense SiC samples were obtained with a homogeneous fine-crystalline microstructure. Results showed that citric acid was an effective dispersant for improving the dispersion of SiC particles containing sintering additives.