Pressureless Sintering of Titanium Diboride with Nickel, Nickel Boride, and Iron Additives

The effect of relatively small additions (1-5 wt%) of nickel, nickel boride (NiB), and iron to promote the liquid-phase sintering of titanium diboride (TiB₂) has been studied. Carbon also was added to some samples, to reduce the amount of oxygen impurities in the TiB₂ ceramics. Green bodies that were formed by uniaxial pressing were sintered in a graphite furnace at 1300°–1700°C, both under vacuum and in a 500 mbar argon atmosphere, and high densities (>94% of theoretical density) were obtained at temperatures greater than or equal to 1500°C. The weight loss of the samples during sintering was shown to be dependent on the densification rate and the final density and was not governed only by the thermodynamics of the system. Significant exaggerated grain growth was observed in samples with nickel, NiB, and iron during sintering at 1700°C. The exaggerated grain growth was observed to be closely related to the oxygen content of the samples and to temperature. The addition of carbon strongly reduced the density and the oxygen content and, thereby, inhibited grain growth. We have proposed that the exaggerated grain growth is enhanced by surface diffusion in a titanium-oxide-rich layer on the TiB₂ grains.     

Microstructure-Mechanical Property Relationships in Hot Isostatically Pressed Alumina and Zirconia-Toughened Alumina

The rates of densification and the mechanical properties of pure Al₂O₃ and ZrO₂-toughened Al₂O₃ (ZTA) have been investigated as a function of the temperatures and time schedules used for hot isostatic pressing (HIP) as a postsintering heat treatment for samples which had already been pressureless sintered in air at 1460°C for 45 min. ZTA hot isostatically presed at 1400°C had a finer grain size and a narrower grain size distribution than ZTA hot isostatically pressed at 1600°C. At both HIP conditions, the density which could be obtained was almost the maximum theoretical density. The amount of grinding-induced and fracture-induced monoclinic ZrO₂ formed as a result of the tetragonal → monoclinic martensitic transformation in ZTA was higher in the samples hot isostatically pressed at 1400°C. ZTA hot isostatically pressed at 1600°C and 100 MPa had fewer flaws and higher strengths than ZTA hot isostatically pressed at 1400°C for the same time, with a gradual improvement in mechanical properties with increasing HIP time at each of these two temperatures. The best mechanical properties were obtained from ZTA hot isostatically pressed at 100 MPa and 1600°C for 1 h: these specimens had a four-point bend strength of 940 ± 15 MPa at room temperature and 540 ± 15 MPa at 1000°C and an indentation fracture toughness at room temperature of 9.4 ± 0.2 MPa·m^1/2.     

Sintering Behavior of Fully Agglomerated Zirconia Compacts

Fully agglomerated superfine zirconia powders were prepared with the coprecipitation and spray-drying method. The compaction of such powders shows no fragmentation of the agglomerates. The sintering behavior of the compacts was studied and two sintering stages were identified: densification within agglomerates at temperatures not higher than 1250°C and the removal of interagglomerate pores at temperatures above 1600°C. The interagglomerate pores are difficult to remove, and sintering between agglomerates even at 1600°C is still insignificant. Heating of the compacts at temperatures above 1600°C leads only to grain growth and the entrapping of pores in large grains.     

Liquid Phase Sintering of Alumina, I. Microstructure Evolution and Densification

The microstructure evolution and densification of alumina containing 10 vol% calcium aluminosilicate glass and 0.5 wt% magnesium oxide sintered at 1600°C were quantified by measuring the evolution of pore-size distribution, the redistribution of liquid phase, and the fraction of closed and open pores. The densification stopped at a limiting relative density during the final stage of sintering, and the small and large pores were filled simultaneously by glass during sintering. In addition, the results indicate that the pressure build-up of the trapped gases in pores causes a significantly negative contribution to the driving force, and consequently the observed reduction in densification during the final stage of liquid phase sintering.     

Hot-Pressing of β-SiC Powder with Al-B-C Additives

The sintering behavior of β-SiC powders with additions of Al, B, and C was studied at 1600° to 1800°C with applied pressures of 20 to 60 MPa. Ceramics with densities of ∼3.08 g/cm³ were obtained by hot-pressing at 1650°C and 50 MPa. The bending strength did not degrade up to 1200°C. A large amount of a second phase, which was apparently Al₈B₄C₇, was observed as streaks in the microstructure. It is suggested that a liquid phase, which coexisted with this compound, enhanced densification.     

Entrapped Gas Effect in the Fast Firing of Yttria-Doped Zirconia

Compared to conventional sintering of Y₂O₃-doped ZrO₂ using a slow heating rate of 10°C/min, microwave sintering and fast firing using a rapid heating rate of about 500°C/min resulted in lower final sintered densities. It is attributed to the residual chlorine in commerical zirconia powders manufactured by the chloride process. By calcining at 1100°C for 1 h to remove residual chlorines from the powder compacts, near full densities (>99% of theoretical) could be obtained by both fast firing and microwave sintering.     

Liquid Phase Sintering of Alumina, III. Effect of Trapped Gases in Pores on Densification

The microstructure evolution and densification kinetics of alumina containing 10 and 20 vol% calcium aluminosilicate glass were studied, for sintering under vacuum and air at 1600°C. Residual porosity was always present in the air-fired samples. The kinetic analysis lent strong support to the notion that trapped gases inhibited the densification and limited the attainment of full density. The samples containing 20 vol% glass were able to reach full density during vacuum sintering. However, the samples containing 10 vol% glass contained some residual porosity even after vacuum sintering, which was attributed to the preferential volatalization of liquid phase.     

Preparation of High-Silica Glasses from Colloidal Gels: II, Sintering

The sintering of dried colloidal SiO₂ gels, whose preparation and properties are reported in Part I, is described. The effects of various sintering parameters were studied and the conditions for achievement of the best optical quality include the use of: a pretreatment of the SiO₂ at ∼925°C, moderate heating rate (∼400°C/h), He+CI₂ atmosphere, 1500° to 1600°C sintering temperature, and 1 to 4 h sintering time. Dynamic sintering kinetic studies (heating rate=400°C/h) show that this SiO₂ sinters to nearly theoretical density by about 1380°C. However, optical transparency is achieved by removal of minor residual porosity at above 1500°C. Isothermal sintering data fit to a model assuming interconnecting cylinders of SiO₂ predict the proper activation energy for the viscosity if initial stages of sintering are considered. Residual porosity in sintered glasses is related to large interstices in the unsintered gel.     

Processing, Fracture Toughness, and Vickers Hardness of Allylhydridopolycarbosilane-Derived Silicon Carbide

Bulk specimens of precursor-derived silicon carbide (SiC) suitable for mechanical-property measurements were prepared from allylhydridopolycarbosilane (AHPCS), which is a commercially available, hyperbranched polycarbosilane. Crack-free pellets were obtained by cold-pressing mixtures of finely ground, 1000°C pyrolyzed, "AHPCS-SiC" with neat AHPCS, followed by pyrolysis to 1000°C and ten subsequent reinfiltration/pyrolysis steps with the neat liquid AHPCS. Then, these pellets were heat-treated to 1200°, 1400°, and 1600°C, followed by additional reinfiltration/pyrolysis cycles to the final respective maximum temperatures. This fabrication process simulated the production of the matrix phase for ceramic-matrix composites via successive infiltration/pyrolysis cycles. The density of the material processed at these temperatures, measured via the Archimedes method, was 2.3, 2.5, 2.6, and 2.9 g/cm³, respectively, and the average open porosities of the samples were 2, 0.2, 1, and 9 vol%, respectively. The fracture toughness was measured using the single-edge V-notched-beam method, and the hardness was measured via Vickers indentation. The samples had an average toughness of 1.40 ± 0.08, 1.65 ± 0.09, 1.67 ± 0.07, and 1.46 ± 0.08 MPa·m^1/2 for the samples that were treated at 1000°, 1200°, 1400°, and 1600°C, respectively. The Vickers hardness for these samples, measured at a load of 1000 g, was 12 ± 1, 13 ± 2, 11 ± 1, and 9 ± 1 GPa, respectively.     

Densification and Thermal Conductivity of AIN Doped with Y2O3, CaO, and Li2O

Small amounts of Li₂O result in sintering in the AIN-Y₂O₃-CaO and AIN-CaO systems at firing temperatures <1600°C. The effect is ascribed to reduction of the liquidus temperature. Furthermore, Li₂O is removed by volatization at temperatures from 1300° to 1600°C, and its content decreases several ppm from the initial 0.3 wt%. Li₂O-doped AIN specimens containing Y₂O₃ and CaO additives are well densified by firing at 1600°C for 6 h, and their thermal conductivity is 135 W^.m^−1.K⁻¹.The effect of Li₂O addition on sintering and thermal conductivity also is discussed through thermo-dynamic considerations.     

Influence of Pyridine–Borane on the Sintering Behavior and Properties of α-Silicon Carbide

In the present study, α-SiC powder is coated with pyridineborane (BH₃·C₅H₅N), a liquid molecular compound, which forms a boron carbonitride (BC_3.5N) layer by heat treatment at 1000°C under argon. The precipitation method leads to an improved chemical homogeneity in the compacted powder resulting in enhanced densification and significant reduction in grain growth during subsequent sintering at temperatures exceeding 2070°C. Thus, small average grain sizes of d ₅₀= 1.3 μm and a narrow grain size distribution ( d ₁₀= 0.6 μm, d ₉₀= 2.2 μm) are detected in the liquid-phase-processed sample sintered at 2200°C for 0.5 h in argon. Final densities of at least 98% of theoretical could be obtained by pressureless sintering at 2100°C. These results as well as the microstructural distribution of the sintering aids in the densified samples are discussed.     

Effects of firing temperature on the microstructures and properties of porous mullite ceramics prepared by foam-gelcasting

Porous mullite ceramics were prepared at 1300–1600°C for 2?h via a foam-gelcasting route using industrial-grade mullite powders as the main raw material, Isobam 104 as the dispersing and gelling agent, triethanolamine lauryl sulphate as the foaming agent and sodium carboxymethyl cellulose as the foam stabilising agent. The effects of firing temperature on the sintering behaviour of green samples as well as microstructures and properties of final porous mullite products were investigated. With increasing the temperature from 1300 to 1600°C, linear shrinkage and bulk density values of fired samples increased, whereas their porosity decreased. Mechanical strength and thermal conductivity values of fired samples decreased with increasing their porosities. Even at a porosity level as high as 79.4%, compressive and flexural strengths of fired samples (with average pore size of 314?μm) remained as high as 9.0 and 3.7?MPa, respectively, and their thermal conductivity (at 200°C) remained as low as 0.21?W?(m^?1?K^?1).     

Spark Plasma Sintered Silicon Nitride Ceramics with High Thermal Conductivity Using MgSiN2 as Additives

Silicon nitride ceramics were prepared by spark plasma sintering (SPS) at temperatures of 1450°–1600°C for 3–12 min, using α-Si₃N₄ powders as raw materials and MgSiN₂ as sintering additives. Almost full density of the sample was achieved after sintering at 1450°C for 6 min, while there was about 80 wt%α-Si₃N₄ phase left in the sintered material. α-Si₃N₄ was completely transformed to β-Si₃N₄ after sintering at 1500°C for 12 min. The thermal conductivity of sintered materials increased with increasing sintering temperature or holding time. Thermal conductivity of 100 W·(m·K)⁻¹ was achieved after sintering at 1600°C for 12 min. The results imply that SPS is an effective and fast method to fabricate β-Si₃N₄ ceramics with high thermal conductivity when appropriate additives are used.     

Effect of Silicon Substitution on the Sintering and Microstructure of Hydroxyapatite

The substitution of between 0 and 1.6 wt% silicon (Si-HA) in hydroxyapatite (HA) inhibited densification at low temperatures (1000°–1150°C), with these effects being more significant as the level of silicon substitution was increased. For higher sintering temperatures (1200°–1300°C), the sintered densities of HA and Si-HA compositions were comparable. Examination of the ceramic microstructures by scanning electron microscopy (SEM) showed that silicon substitution also inhibited grain growth at higher sintering temperatures (1200°–1300°C). The negative effect of silicon substitution on the sintering of HA at low temperatures (1000°–1150°C) was reflected in the hardness values of the ceramics. However, for higher sintering temperatures, e.g., 1300°C, where sintered densities were comparable, the hardness values of Si-HA compositions were equal to or greater than that of HA, reflecting the smaller grain sizes observed for the former.     

Temperature Dependence in Air of Fe2+ Concentration and Its Relation to Electrical Conductivity in a Natural Eastern Coal Slag

Ferrous iron concentration in a coal slag obtained from Bow, New Hampshire, was studied as a function of heat treatment in air. Results indicate that the concentration varies continuously between 1300° and 1600°C, the slag becoming more oxidized as the temperature drops from 1600°C. For lower temperatures at which the slag is solid or highly viscous, oxidation still occurs between 1300° and 900°C when the coal slag is cooled slowly from temperatures above 1300°C. No such change is observed for fast quenches. This interpretation is consistent with observed dc electrical conductivity data obtained from similar samples.     

Porous 2H-Silicon Carbide Ceramics Fabricated by Carbothermal Reaction between Silicon Nitride and Carbon

Porous SiC ceramics were synthesized by sintering pressed and pressed/CIPed powder compacts of α-Si₃N₄, carbon (Si₃N₄:C = 1:3 mol as ratio), and sintering aids, at 1600°C for few hours to achieve a reaction, and subsequently sintering at a temperature range of 1750°–1900°C, in an argon atmosphere. High porosities from 45%–65% were achieved by low shrinkage with large weight loss. Formation of pure 2H-SiC phase via a reaction between Si₃N₄ and carbon can be demonstrated by X-ray diffractometry. The resultant porous SiC samples were characterized by SiC grain microstructures, pore-size distribution, and flexural strength. This method has the advantage of fabricating high-porous SiC ceramics with fine microstructure and good properties at a relatively low temperature.     

Microstructural Evolution during Pressureless Sintering of Lead Lanthanum Zirconate Titanate Ceramics with Excess Lead(II) Oxide

The early stages of sintering of lead lanthanum zirconate titanate (PLZT) 9/65/35 ^† ceramics prepared with 10 wt% excess PbO were monitored by quenching uniaxially pressed pellets after a variety of heat treatments. TEM revealed a PbO-rich amorphous film covering the particle surfaces and interparticle porosity in pellets quenched after 5 min at 1125° to 1180°C. This amorphous phase is indicative of the presence of a high-temperature liquid phase with composition approximately Pb_0.87Zr_0.15Ti_0.04O_1.19. The liquid composition moves toward the PbO-TiO₂ eutectic as sintering progresses. After 10 to 30 min at 1180°C, the liquid composition was approximately Pb_0.9Zr_0.04Yi_0.06O_l.1 and crystallized on quenching. High densities of dislocations with = 1/2〈110〉 and low-angle boundaries were observed in samples quenched from 1180°C after 10 to 30 min. Mechanisms for the formation of these dislocations are suggested.     

Microwave Sintering of Alumina at 2.45 GHz

The sintering kinetics and microstructural evolution of alumina tubes (∼17 mm length, ∼9 mm inner diameter, and ∼11 mm outer diameter) were studied by conventional and microwave heating at 2.45 GHz. Temperature during microwave heating was measured with an infrared pyrometer and was calibrated to ±10°C. With no hold at sintering temperature, microwave-sintered samples reached 95% density at 1350°C versus 1600°C for conventionally heated samples. The activation energy for microwave sintering was 85 ± 10 kJ/mol, whereas the activation energy for conventionally sintered samples was 520 ± 14 kJ/mol. Despite the difference in temperature, grains grew from ∼1.0 μm at 86% density to ∼2.6 μm at 98% density for both conventionally sintered and microwave-sintered samples. The grain size/density trajectory was independent of the heating source. It is concluded that the enhanced densification with microwave heating is not a consequence of fast-firing and therefore is not a result in the change in the relative rates of surface and grain boundary diffusion in the presence of microwave energy.     

Densification and Mechanical Behavior of HfC and HfB2 Fabricated by Spark Plasma Sintering

Hafnium diboride (HfB₂)- and hafnium carbide (HfC)-based materials containing MoSi₂ as sintering aid in the volumetric range 1%–9% were densified by spark plasma sintering at temperatures between 1750° and 1950°C. Fully dense samples were obtained with an initial MoSi₂ content of 3 and 9 vol% at 1750°–1800°C. When the doping level was reduced, it was necessary to raise the sintering temperature in order to obtain samples with densities higher than 97%. Undoped powders had to be sintered at 2100°–2200°C. For doped materials, fine microstructures were obtained when the thermal treatment was lower than 1850°C. Silicon carbide formation was observed in both carbide- and boride-based materials. Nanoindentation hardness values were in the range of 25–28 GPa and were independent of the starting composition. The nanoindentation Young's modulus and the fracture toughness of the HfB₂-based materials were higher than those of the HfC-based materials. The flexural strength of the HfB₂-based material with 9 vol% of MoSi₂ was higher at 1500°C than at room temperature.     

Experimental Analysis of Sintering of MgO Compacts

Experimental sintering studies On undoped and cao-doped Mgo powder compacts in Static air and flowing Water Vapor atmospheres were conducted at 1230° to 1600°C. Corresponding microstructural changes of specimens during sintering were examined by scanning electron microscopy. Kinetic and microstructural data were analyzed to determine sintering mechanisms during the initial and intermediate stages of sintering.