Crystallization Behavior of Amorphous Silicon Carbonitride Ceramics Derived from Organometallic Precursors

The crystallization behavior of organometallic-precursor-derived amorphous Si-C-N ceramics was investigated under N₂ atmosphere using X-ray diffractometry (XRD), transmission electron microscopy (TEM), and solid-state ²⁹Si nuclear magnetic resonance (NMR) spectroscopy. Amorphous Si-C-N ceramics with a C/Si atomic ratio in the range of 0.34–1.13 were prepared using polycarbosilane-polysilazane blends, single-source polysilazanes, and single-source polysilylcarbodiimides. The XRD study indicated that the crystallization temperature of Si₃N₄ increased consistently with the C/Si atomic ratio and reached 1500°C at C/Si atomic ratios ranging from 0.53 to 1.13. This temperature was 300°C higher than that of the carbon-free amorphous Si-N material. In contrast, the SiC crystallization temperature showed no clear relation with the C/Si atomic ratio. The TEM and NMR analyses revealed that the crystallization of amorphous Si-C-N was governed by carbon content, chemical homogeneity, and molecular structure of the amorphous Si-C-N network.     

Change of Crystal Phases and Microstructure of Amorphous Si-C-N Powder by Hot Pressing

An amorphous Si-C-N powder with Y₂O₃ and Al₂O₃ powder as sintering additives was hot-pressed at 1900°C for 120 min in a nitrogen atmosphere. Changes in the crystalline phases and microstructure of the amorphous Si-C-N powder during sintering were investigated by X-ray diffractometry (XRD) and transmission electron microscopy (TEM). The defects at the fracture origins of the sintered bodies after bending tests also were investigated by scanning electron microscopy (SEM) and electron probe microanalysis (EPMA). XRD showed that alpha-Si₃N₄ was formed initially from the amorphous Si-C-N by 1530°C, which then transformed to ß-Si₃N₄ at 1600°C. Also, a slight formation of crystalline SiC occurred during the transformation from alpha- to ß-Si₃N₄, and it increased after the transformation was completed at 1900°C. TEM revealed that many SiC nanoparticles were incorporated into ß-Si₃N₄ grains after the transformation from alpha- to ß-Si₃N₄ at 1600°C. They were located at the triple points of the grain boundaries of ß-Si₃N₄ after continued Si₃N₄ grain growth at 1900°C. Besides the SiC nanoparticles, large agglomerations of carbon or SiC particles of 20-60 µm size were observed by SEM and EPMA at the fracture origins of the sintered bodies after the bending tests.     

Processing Aluminum Nitride-Silicon Carbide Composites via Polymer Infiltration and Pyrolysis of Polymethylsilane, a Precursor to Stoichiometric Silicon Carbide

AlN-SiC-particle-reinforced composites have been prepared at lessthan equal to1400°C using submicrometer AlN, -325 mesh alpha-SiC particles, and polymethylsilane (PMS; -(CH₃SiH) _n -) via a polymer infiltration and pyrolysis (PIP) process. PMS is an organometallic SiC polymer precursor that can be modified with 16 wt% cross-linking aid to provide mPMS. mPMS converts to nanocrystalline β-SiC with >80% ceramic yield (1000°C in argon) with some excess (<5 wt%) graphitic carbon. mPMS has been used successfully as a nonfugitive binder for AlN-SiC compacts. Densities of 2.5 versus 2.1 g/cm³ have been obtained after nine PIP cycles for disk-shaped compacts formulated with and without mPMS binder, respectively. alpha-SiC seeds crystallization of β-SiC derived from mPMS at temperatures as low as 1000°C. Some evidence suggests that AlN-SiC solid solutions form at particle/matrix interfaces.     

Spontaneous Infiltration of Iron Silicides into Silicon Carbide Powder Preforms

The infiltration of liquid Fe₃Si (mp of ∼1300°C), Fe₅Si₃ (mp of ∼1210°C), and FeSi (mp of ∼1410°C) into SiC powder preforms was performed at various infiltration temperatures for 60 min under either argon flow or dynamic vacuum. The amount of infiltration under various infiltration conditions was studied as a function of infiltration temperature. For the preforms as-pressed from raw SiC powder, the amount of infiltration of the three silicides under argon flow was independent of their melting points, but suddenly increased within a common temperature range from 1450° to 1550°C. Thermodynamic analyses indicated that the common temperature range corresponded to the temperature at which the SiO₂ on the surface of the SiC particles was decreased under argon flow. Infrared spectroscopy showed SiO₂ on the surfaces of as-received SiC powder particles, but not on the surfaces of the SiC powder particles fired under argon at 1600°C. The amount of infiltration of the as-pressed SiC under vacuum and of fired SiC under argon and vacuum exhibited an obvious dependence on the silicide melting points. This was attributed to the SiO₂ reduction taking place at temperatures lower than the melting points of the silicides. The amount of infiltration was then controlled by the melt viscosity.     

Transmission Electron Microscopy and Electron Energy-Loss Spectroscopy Study of Nonstoichiometric Silicon-Carbon-Oxygen Glasses

Crystallization behavior of Si-C-O glasses in the temperature range of 1000°–1400°C was investigated using transmission electron microscopy (TEM) in conjunction with electron energy-loss spectroscopy (EELS). Si-C-O glasses were prepared by pyrolysis of polysiloxane networks obtained from homogeneous mixtures of triethoxysilane, T^H, and methyldiethoxysilane, D^H. Si-C-O glass composition depended on the molar ratio of the precursors utilized. At a ratio of T^H/D^H= 1, the formation of a carbon-rich glass was observed, whereas a ratio of T^H/D^H= 9 yielded a Si-C-O glass with excess free silicon. Both materials were amorphous at 1000°C, but showed a distinct difference in crystallization behavior on annealing at high temperature. Although T^H/D^H= 1 revealed a small volume fraction of SiC precipitates in addition to a very small amount of residual free carbon at 1400°C, T^H/D^H= 9 showed, in addition to SiC crystallites, numerous larger silicon precipitates (20–50 nm), even at 1200°C. Both materials underwent a phase separation process, SiC _x O_2(1-x)→ x SiC + (1 - x )SiO₂, when annealed at temperatures exceeding 1200°C.     

Synthesis of Silicon Nitride/Silicon Carbide Nanocomposite Powders through Partial Reduction of Silicon Nitride by Pyrolyzed Carbon

An alternative method to incorporate nanometer-sized silicon carbide (SiC) particles into silicon nitride (Si₃N₄) powder was proposed and investigated experimentally. Novolac-type phenolic resin was dissolved in ethanol and mixed with Si₃N₄ powder. After drying and curing, the resin was converted to reactive carbon via pyrolysis. Si₃N₄ powder was partially reduced carbothermally using the pyrolyzed carbon, and nanometer-sized SiC particles were produced in situ at 1530°-1610°C in atmospheric nitrogen. At temperatures <1550°C, the reduction rate was low and the SiC particles were very small; no SiC whiskers or barlike SiC was observed. At 1600°C, the reduction rate was high and the reaction was close to completion after only 10 min, with the appearance of SiC whiskers as well as curved, barlike, and equiaxial SiC, all of which were dozens of nanometers in diameter; this size is greater than that at observed temperatures <1550°C. A longer soaking time at 1600°C led to agglomerates. SiC particles were close to the surface of the Si₃N₄ particles. The SiC content could be adjusted by changing the carbon content before reduction and the reduction temperature. A reaction mechanism that involved the decomposition of Si₃N₄ has been proposed.     

Bismuth Titanate from Mechanical Activation of a Chemically Coprecipitated Precursor

Most of the chemistry-based preparation routes for bismuth titanate (BIT) involve calcination at elevated temperatures in order to realize precursor-to-ceramic conversion. In a completely different approach using an amorphous BIT hydroxide precursor, nanocrystalline particles of layered perovskite BIT are synthesized by mechanical activation, skipping the detrimental crystallite coarsening and particle aggregation encountered at high temperatures. Mechanical activation leads to nucleation and steady growth of BIT crystallites in the amorphous precursor matrix, while Bi₂O₃ is involved as an intermediate transitional phase. The activation-derived BIT particles demonstrate a rounded morphology of ∼50 nm in size. This is in contrast to the BIT derived from calcination of the coprecipitated precursor at 600°C that is dominated by coarsened platelike particles. The former is sintered to a density of >95% theoretical at 875°C for 2 h, leading to a dielectric constant of ∼1260 when measured at 1 MHz and the Curie temperature of 646°C.     

Hydrothermal Synthesis of Bismuth Titanate Powders

Bismuth titanate was synthesized under hydrothermal conditions from an amorphous bismuth–titanium precursor gel. The gel was formed by mixing a bismuth acetate complex with titanium butoxide and then adding the solution dropwise into 6 M NaOH. The resulting gel suspension was reacted under hydrothermal conditions at temperatures ranging from 160° to 200°C to form crystalline bismuth titanate. The gel crystallization kinetics increased with temperature, which resulted in 100% crystalline bismuth titanate in 5 h at 200°C. Wavelength-dispersive spectroscopy data indicated that sodium was incorporated into bismuth titanate during processing, and X-ray diffractometry suggested that the powder was composed of the Bi₅Ti₄O₁₅ phase. Transmission electron microscopy micrographs showed that the gel particles decomposed to 100–200 nm crystalline bismuth titanate particles during hydrothermal processing.     

Effect of Silicon Carbide Additions on the Crystallization Behavior of a Magnesia-Lithia-Alumina-Silica Glass

Glass in the MgO-Li₂O-A1₂O₃-SiO₂ system was observed to crystallize readily at temperatures from 700° to 900°C. The primary crystalline phase evolved was Li₂Si₂O₅, and the secondary phase evolved was Li₂SiO₃. The glass was amorphous after heating in air at 1050°C for 30 min. The addition of 0.5 wt% SiC powder resulted in the crystallization of Li₂SiO₃ during heating in air at 1050°C for 30 min. It was suggested that the difference in crystallization behavior with Sic addition was due to dissolution of Sic into the oxide glass.     

Reaction Bonding and Mechanical Properties of Mullite/Silicon Carbide Composites

Based on the RBAO technology, low-shrinkage mullite/SiC/ Al₂O₃/ZrO₂ composites were fabricated. A powder mixture of 40 vol% Al, 30 vol% A1₂O₃ and 30 vol% SiC was attrition milled in acetone with TZP balls which introduced a substantial ZrO₂ wear debris into the mixture. The precursor powder was isopressed at 300–900 MPa and heattreated in air by two different cycles resulting in various phase ratios in the final products. During heating, Al oxidizes to Al₂O₃ completely, while SiC oxidizes to SiO₂ only on its surface. Fast densification (at >1300°C) and mullite formation (at 1400°C) prevent further oxidation of the SiC particles. Because of the volume expansion associated with the oxidation of Al (28%), SiC (108%), and the mullitization (4.2%), sintering shrinkage is effectively compensated. The reaction-bonded composites exhibit low linear shrinkages and high strengths: shrinkages of 7.2%, 4.8%, and 3%, and strengths of 610, 580, and 490 MPa, corresponding to compaction pressure of 300, 600, and 900 MPa, respectively, were achieved in samples containing 49–55 vol% mullite. HIPing improved significantly the mechanical properties: a fracture strength of 490 MPa and a toughness of 4.1 MPa^.m^1/2 increased to 890 MPa and 6 MPa^.m^1/2, respectively.     

Tensile Ductility of Superplastic Al2O3–Y2O3–Si3N4/SiC Composites

Si₃N₄/SiC composites are ceramic materials that exhibit excellent performance for high-temperature applications. Prepared from an ultrafine amorphous Si-C-N powder, sintered materials are constituted mainly of a β -Si₃N₄ matrix with SiC inclusions and have a very small grain size (less than 1 μm). Such a microstructure is propitious for superplastic forming. Superplasticity has been studied in tension, from 1550° to 1650°C, under nitrogen atmosphere. Elongations over 100% have been achieved. In many cases, at the highest temperatures and slowest strain rates, materials are damaged by different processes, including microcracking, cavitation, and chemical decomposition. A map of the most suitable (strain-rate/temperature) domain has been established. It allows the prevention of any structural alteration by selecting carefully the testing conditions. Since specimens suffered considerable strain-induced hardening, sources for this phenomenon are examined. Although the experiments have involved high temperature and extensive strain, neither static nor dynamic grain growth has occurred. Crystallization of the amorphous grain-boundary phase, which is reported in most cases, may be invoked. However, based on microstructural observations, it is not the unique origin for flow hardening.     

Carbothermal Reaction of Silica–Phenol Resin Hybrid Gels to Produce Silicon Nitride/Silicon Carbide Nanocomposite Powders

A carbothermal reaction of silica–phenol resin hybrid gels prepared from a two-step sol–gel process was conducted in atmospheric nitrogen. The gels were first pyrolyzed into homogeneous silica–carbon mixtures during heating and subsequently underwent a carbothermal reaction at higher temperatures. Using a gel-derived precursor with a C/SiO₂ molar ratio higher than 3.0, Si₃N₄/SiC nanocomposite powders were produced at 1500°–1550°C, above the Si₃N₄–SiC boundary temperature. The predominant phase was Si₃N₄ at 1500°C, and SiC at 1550°C. The Si₃N₄ and SiC phase contents were adjustable by varying the temperature in this narrow range. The phase contents could also be adjusted by changing the starting carbon contents, or by its combination with varying reaction temperature. A two-stage process, i.e., a reaction first at 1550°C and then at 1500°C, offered another means of simple and effective control of the phase composition: the Si₃N₄ and SiC contents varied almost linearly with the variation of the holding time at 1550°C. The SiC was nanosized (∼13 nm, Scherrer method) formed via a solid–gas reaction, while the Si₃N₄ has two morphologies: elongated microsized crystals and nanosized crystallites, with the former crystallized via a gaseous reaction, and the latter formed via a solid–gas reaction. The addition of a Si₃N₄ powder as a seed to the starting gel effectively reduced the size of the Si₃N₄ produced.     

Nanostructured Dense ZrO2 Thin Films from Nanoparticles Obtained by Emulsion Precipitation

Nonagglomerated spherical ZrO₂ particles of 5–8 nm size were made by emulsion precipitation. Their crystallization and film-forming characteristics were investigated and compared with nanosized ZrO₂ powders obtained by sol–gel precipitation. High-temperature X-ray diffraction indicated that the emulsion-derived particles are amorphous and crystallize at 500°C into tetragonal zirconia, which is stable up to 1000°C. Crystallite growth from 5–20 nm occurred between 500°–900°C. Films of 6–75 nm thickness were made by spreading, spin coating, and controlled deposition techniques and annealed at 500°–600°C. The occurrence of t -ZrO₂ in the emulsion-precipitated powder is explained by the low degree of agglomeration and the corresponding low coarsening on heating to 500°–800°C, whereas the agglomerated state of the sol–gel precipitate powder favors the occurrence of the monoclinic form of zirconia under similar conditions.     

Preparation and Characterization of Submicron Hafnium Oxide

Submicron hafnium oxide powder prepared by hydrolytic decomposition of alkoxides was studied. The particle size range of this powder was 10 to 50 Å. Emission spectrographic analysis of the powder after it was calcined at 250°C for 0.5 h indicated a purity of >99.995%. Up to 320°C, the powder showed no crystallinity by X-ray analysis. The amorphous HfO₂ was isothermally aged at 5° to 10°C intervals between 200° and 500°C. X-ray diffraction patterns indicate a sharp transition from an amorphous state to the monoclinic phase at 325°C. High-temperature X-ray studies and DTA suggest nucleation and growth of small crystallites at 420°C leading to conversion to monoclinic HfO₂ at 480°C. BET surface area measurements and TGA of the powders were also conducted. A powder which transformed at 325°C to the monoclinic phase was isothermally aged below 325°C for 150 h without change.     

Fabrication of Grain-Oriented Bi2WO6 Ceramics

Grain-oriented Bi₂WO₆ ceramics were fabricated by normal sintering techniques. Platelike crystallites were initially synthesized by a fused salt process using an NaCl-KCI melt. When calcined at <800°C, the Bi₂WO₆ crystallites are 3∼5 μ m in size and, at >850°C, =100 μm. After dissolving away the salt matrix, the Bi₂WO₆ particles were mixed with an organic binder and tapecast to align the platelike crystallites. Large particles were easily oriented by tapecasting but the sinterability of the tape was poor. Preferred orientation of small particles was increased by tapecasting and grain growth during sintering further improves the degree of orientation. Sintering above the 950°C phase transition, however, results in discontinuous grain growth and low densities. Optimum conditions for obtaining highly oriented ceramics with high density occur at sintering temperatures of 900°C using fine-grained powders which yield orientation factors of =0.88 and densities of 94% theoretical.     

Formation of Silicone Carbide Membrane by Radiation Curing of Polycarbosilane and Polyvinylsilane and its Gas Separation up to 250°C

Silicon carbide (SiC) ceramic coating was developed from precursor polymer blend of polycarbosilane and polyvinylsilane on porous alumina substrate by radiation curing. The polymers were crosslinked with oxygen present in the atmosphere during irradiation and pyrolyzed at 850°C in order to convert the polymer into SiC ceramics. Fabricated SiC film was used as a membrane for gas separation, achieving high separation ratios of 206 for H₂ and 241 for He over the nitrogen at 250°C.     

Low-Temperature High-Pressure Consolidation of Amorphous Al2O3–15 mol% Y2O3

This study examined pressure consolidation of amorphous Al₂O₃–15 mol% Y₂O₃ powders prepared by co-precipitation and spray pyrolysis. The two amorphous powders had similar true densities and crystallization sequences. Uniaxial hot pressing was carried out at 450°–600°C with a moderate pressure of 750 MPa. The co-precipitated powder could be hot pressed to a maximum relative density of 98% and remained amorphous. Pressure adversely affected the densification of the spray-pyrolyzed powder by favoring an early crystallization of γ-Al₂O₃ phase at 580°C. Plastic deformation of the amorphous phase is believed to be responsible for the large densification of the amorphous powders.     

New Strategies for Preparing NanoSized Silicon Nitride Ceramics

We report the preparation of nanosized silicon nitride (Si₃N₄) ceramics via high-energy mechanical milling and subsequent spark plasma sintering. A starting powder mixture consisting of ultrafine β-Si₃N₄ and sintering additives of 5-mol% Y₂O₃ and 2-mol% Al₂O₃ was prepared by high-energy mechanical milling. After milling, the powder mixture was mostly transformed into a non-equilibrium amorphous phase containing a large quantity of well-dispersed nanocrystalline β-Si₃N₄ particles. This powder precursor was then consolidated by spark plasma sintering at a temperature as low as 1600°C for 5 min at a heating rate of 300°C/min. The fully densified sample consisted of homogeneous nano-Si₃N₄ grains with an average diameter of about 70 nm, which led to noticeable high-temperature ductility and elevated hardness.     

Simple Synthesis of Submicrometer Lead Titanate Powder by Precipitation of TiO2 Precursor on PbO Particulates

A simple way to prepare phase-pure, submicrometer PbTiO₃ powder was tried by precipitation. Precipitation was carried out in an aqueous PbO slurry using aqueous TiCl₄ and dilute NH₄OH at pH 9.5 ± 0.1. The TG/DSC curves of the PT precursor show weight loss of ∼7% and two exotherms at 492° and 522°C. They are attributed to the crystallization of tetragonal PbTiO₃. XRD shows that tetragonal PbTiO₃ can be obtained by heat treatment around 500°C via a noncrystalline state. SEM shows that the PbTiO₃ powder calcined at 600°C for 1 h is well crystallized and in the range of 100—300 nm.     

Silicon Nitride–Silicon Carbide Nancocomposites Fabricated by Electric-Field-Assisted Sintering

Starting with Si-C-N(-O) amorphous powders, and using the electric field assisted sintering (EFAS) technique, silicon nitride/silicon carbide nanocomposites were fabricated with yttria as an additive. It was found that the material could be sintered in a relatively short time (10 min at 1600°C) to satisfactory densities (2.96–3.09 g/cm³) using 1–8 wt% yttria. With decreasing yttria content, the ratio of SiC to Si₃N₄ increased, whereas the grain size decreased from ∼150 nm to as small as 38 nm. This offers an attractive way to make nano-nanocomposites of silicon nitride and silicon carbide.