Synthesis of Si3N4 using sepiolite and various sources of carbon

Sepiolite of Turkish origin was used as Si precursor in the syntheses of silicon nitride (Si₃N₄) powders by carbothermal reduction-nitridation (CRN) by mixing with several reducing agents i.e. charcoal, carbon black and petroleum coke as discrete particles and acrylonitrile as an intercalation medium. Purified sepiolite samples with a pre-determined C/SiO₂ ratio of 4 yielded Si₃N₄ powders after firing at temperatures 1300–1475°C under continuous nitrogen flow. The various sepiolite-reducing agent combinations were evaluated. The / ratio and secondary phase content of the powders after CRN were found to depend on temperature, time, heating rate and on the physicochemical properties of the precursor used such as, surface area and mixing of the reactants.     

Thermal conductivity of unidirectionally oriented Si3N4w/Si3N4 composites

-silicon nitride whiskers were aligned unidirectionally in silicon nitride sintered with 2 wt% Al₂O₃ and 6 wt% Y₂O₃. It was be densified by the Gas Pressure Sintering (GPS) method. Thermal conductivity of the sintered body with different amount of - silicon nitride whiskers was measured by the direct contact method from 298 K to 373 K. This unidirectionally oriented -silicon nitride whiskers grew into the large elongated grains, and improved also the thermal conductivity. The amount of -silicon nitride whiskers changed the microstrcuture, which changed the thermal conductivity.     

Chemical vapour deposition of silicon nitride in a microwave plasma assisted reactor

Microwave plasma assisted chemical vapour deposition was used to produce silicon nitride films on silicon substrates from mixtures of methane and nitrogen. Deposition temperatures varied from 800 to 1000°C and pressure varied from 53.2 to 79.8×10²Pa. Gas mixtures with low methane content resulted in no reaction. Gas mixtures with high methane content produced an amorphous carbon film on the silicon wafer surface. At intermediate methane contents, the process produces a mixture of and silicon nitride. A mechanism is proposed according to which the silicon surface is chemically etched by the activated methyl radicals forming Si(CH₃)₄, which then reacts with nitrogen atoms (or ions) to form the silicon nitride. The morphology of the individual crystals evolves from platelets to needle-like depending on the deposition conditions, and on the surface coverage of the silicon surface.     

Sinterability of β-SiAlON powder prepared by carbothermal reduction and simultaneous nitridation of ultrafine powder in the Al2O3-SiO2 system

Three types of -SiAlON (Si_{6 – z} Al _z O _z N_{8 – z} ) powder were prepared by the carbothermal reduction and simultaneous nitridation of ultrafine powders in the Al₂O₃-SiO₂ system. The ultrafine starting oxide powders, prepared using the vapour-phase reaction technique, were mixed with carbon powder and heated at 1400 °C for 1 h under flowing nitrogen to form -SiAlON and followed by heating at 570 °C for 1 h in air to remove residual carbon. The resulting powders contained only -SiAlON with z values of 1.63, 2.05, and 2.99. The relative density (bulk density/true density) of -SiAlON compacts pressureless sintered at 1800 °C for 1 h under flowing nitrogen increased with z and reached 89.9% at z = 2.99. When the -SiAlON compact with z = 2.99 was hot pressed at 1800 °C for 1 h under flowing nitrogen, a maximum relative density of 93.6% was achieved. Although this hot pressed compact contained a small amount of 15R-SiAlON in addition to -SiAlON, it possessed a small average grain size (typically 0.5 m diameter) and high Vickers hardness (19.2 GPa).     

Microstructure and grain-boundary characterization of HIP'ed high-purity silicon nitride

Laser synthesized, ultrafine silicon nitride was densified via hot isostatic pressing (HIP'ing) without any oxide-sintering-aid additions. HIP'ing was performed on exposed samples made from powder that had been exposed to the atmosphere, thereby picking up an oxide surface layer; and unexposed samples made from powders processed entirely under glove-box conditions, i.e. with minimal oxygen contamination. High-resolution transmission electron microscopy (TEM) studies indicate that the exposed Si₃N₄ powder samples, HIP'ed at temperatures in excess of the melting point of SiO₂, densified via a solution-reprecipitation mechanism, with an intergranular glassy phase of high-purity SiO₂. In contrast, samples of unexposed Si₃N₄ powder had to be HIP'ed to 2050°C to achieve a density of 70%_Th (where _Th is the theoretical density of silicon nitride). In this state, the sample consisted of equiaxed -Si₃N₄ grains, with localized high-density regions. These regions had clean grain boundaries.     

Effects of promoters on the product quality of nanophase SiC/α-Si3N4 composite powders synthesized through carbothermal reduction nitridation

The effect of additives is investigated for the carbothermal reduction synthesis of nanophase silicon carbide/silicon nitride composite powders. Mixtures of silica, carbon, seed silicon nitride, and additive are reacted in a thermogravimetric analyzer. The mass loss information combined with compositional and spectroscopic analysis allows product quality (morphology, surface area, -Si₃N₄ and -SiC contents, oxygen content, etc.) information to be obtained. It was observed that all of the additives used in this study increased the reaction rate. Lithium carbonate produced a silicon nitride/silicon carbide composite that was not significantly different from experiments without promoter. However, the product quality was severely affected in other instances.     

Study of the preparation process for BaO-Al2O3-SiO2 powders by a two-step method

BaO-SiO₂ and Al₂O₃-SiO₂ dried gel powders were prepared by the sol-gel process using TEOS, aluminium nitrate and barium acetate as raw materials. By using these starting materials, -BaAl₂Si₂O₈ (hexacelsian) powders with small particle size were obtained after calcining at 1000 °C. The effects of solvents and prehydrolysis of TEOS on the gelation were studied. The physical and chemical changes, and phase transformation of the gel powders for BaO (Al₂O₃)-SiO₂ and BaO-Al₂O₃-SiO₂ systems during heating were examined using differential thermal analysis, gas chromatography and X-ray diffraction. The particle sizes of the gel powders obtained were also observed by SEM and TEM.     

Influence of powder characteristics on gas pressure sintering of Si3N4

The sintering behaviours of four kinds of Si₃N₄ powders were investigated by dilatometry in 10 atm N₂ at 1890, 1930 and 2050° C. The sinterabilities of powders were compared and discussed in relation to the powder characteristics. A large size distribution in the powder accelerated grain and pore growth at <1800° C, which resulted in the inhibition of further densification at >1800° C. The presence of carbon in a powder prevented densification. A powder with a uniform grain size kept the microstructure of the sintered material uniform during sintering at <1800° C and gave a high degree of shrinkage at >1800° C. Densification at >1800° C was accompanied by the dissolution of equi-axial -Si₃N₄ grains and reprecipitation as elongated -Si₃N₄ grains from the oxynitride liquid. The relation between the densification and microstructure is discussed in terms of the relative rates of densification and grain growth.     

Dense single-phase β-sialon ceramics by glass-encapsulated hot isostatic pressing

Single phase-sialon ceramics, Si_6–z Al _z O _z N_8–z , have been prepared from carefully balanced powder mixtures, also taking account of any excess oxygen in the starting materials. Sintering powder compacts in a nitrogen atmosphere (0.1 MPa) at 1800° C or higher transforms the starting mixture into a-sialon solid solution atz-values up to about 4.3, but the sintered material has an open porosity. Addition of 1 wt% Y₂O₃ to the starting mix improved the sintering behaviour somewhat and the density of the sintered compacts reached 95% of the theoretical value. By glass-encapsulated hot isostatic pressing at 1825° C, however, sintered materials of virtually theoretical density could be obtained, with or without the 1 wt% Y₂O₃ addition. These latter samples have been studied by X-ray diffraction and electron microscopy, and their hardness and indentation fracture toughness have been measured. It was found that the maximum extension of the-sialon phase composition at 1825° C and 200 MPa pressure is slightly below 4,z 3.85 and about 4.1 at atmospheric pressure, and that the hexagonal unit cell parameters are linear functions of thez-value. The single-phase-sialon ceramics had no residual glassy grain-boundary phase. The grain shape was equi-axed and the grain size increased from about 1m at lowz-values to 5m at highz-values. At lowz-values the hardness at a 98 N load was 1700 and the fracture toughness 3, whereas an increase inz above 1 caused both the hardness and fracture toughness to decrease significantly. Addition of 1 wt % Y₂O₃ to the starting mix prior to the HIP-sintering gave rise to a small amount of amorphous intergranular phase, changes in grain size and shape, a clear increase in fracture toughness and a moderate decrease in hardness.     

Crystallization of some spodumene-lithium zinc orthosilicate glasses

By using thermal analysis, X-ray diffraction, polarizing and electron microscopy the effect of compositional variation, thermal treatment and nucleation catalysts TiO₂ and ZrO₂ on the nature, type and stability fields of the crystallizing phases, as well as the resulting microstructures, is described for some stoichiometric glass compositions within the system LiAlSi₂O₆-Li₂ZnSiO₄. Intense uniform volume crystallization was achieved. Transparent glass-ceramics with ultrafine microstructures could also be obtained at temperatures near 700 °C. Crystallization begins with the formation of a proto - and/or _II-Li₂ZnSiO₄ followed by, or concomitant with, -eucryptite ss. The proto -phase was formed over a narrow temperature range and rapidly transformed into its _II-modification which, although showing a wider stability range, ultimately transformed into the stable _o-modification. The metastable -eucryptite ss starts its transformation into -spodumene around 800 °C. By prolonged heating at temperatures as high as 1000–1040 °C, -spodumene and _o-Li₂ZnSiO₄ were the main stable end products. TiO₂ and ZrO₂ have contrasting effects on the stability of the LiZn orthosilicates and -eucryptite ss -spodumene transformations. The former exhibits a catalytic effect and the latter showed a retarding effect on these processes.     

Sintering and mechanical properties of β-wollastonite

Detailed microstructural studies have been carried out on porous -wollastonite (CaSiO₃) ceramics with 40–60% of the theoretical density. Xonotlite (Ca₆Si₆O₁₇(OH)₂) was used as starting material, and the reaction and sintering behaviour were systematically examined in the range 800–1200 °C in air. Analysis of the mechanical properties showed that the strength degradation of -wollastonite ceramics was certainly induced by the change of microstructure. Isothermal annealing at 1100 °C, however, did not preferentially affect the microstructure or the mechanical properties of sintered -wollastonite. These observations lead to the conclusion that the measured bending strength and Vickers hardness of porous -wollastonite ceramics can be substantially modified and improved by controlling the microstructure, in particular due to the shape of randomly oriented grains in the matrix.     

Structural evolution during mechanical alloying and annealing of a Nb-25at%Al alloy

Mixtures of pure elemental Al and Nb powders of Nb-25at%Al composition was mechanically alloyed, and structural evolution during high energy ball milling has been examined. Al dissolved in Nb from the early stage of the ball milling, and amorphization became noticeable after longer than five hours of milling. However the dissolution of Al in Nb was not completed before the amorphization. No intermetallic phase formed during the mechanical alloying. Before complete amorphization, metastable nitride of Nb_4.62N_2.14 (i.e., -NbN) with hexagonal structure has formed in nanocrystalline size through nitrogen incorporation from ambient environment. The lattice parameter of Nb increased significantly (up to 3.3433 Å after 5 hours of milling) during the milling. Upon annealing above 950 °C, Nb₂Al became the dominant feature with the -NbN, and Nb₃Al did not form from the samples milled at ambient environment. Nb₃Al appeared only from a sample milled at Ar environment. Structural evolution during mechanical alloying of the Nb-Al system is critically dependent the upon milling environment.     

A mechanism for the nitridation of Fe-contaminated silicon

The influence of iron impurity on both the oxidation and nitridation of high purity silicon has been investigated. It is shown that iron is effective in rapidly removing the protective silica film which normally covers silicon. Experimental evidence suggests that the removal is achieved by iron-induced devitrification and disruption of the silica, thus allowing the SiO (g) generated by the Si/SiO₂ interface reaction to escape. During the nitridation of iron-contaminated silicon powder compacts it is found that iron significantly enhances the extent of reaction for contamination levels of <1000 p.p.m. Fe (by weight). Above this level there is a decrease in the rate of formation of extra nitride. At all levels of contamination the percentage of silicon converted to -Si₃N₄ was observed to be directly proportional to the iron concentration, and it is shown that this -growth occurs within an FeSi_x liquid phase. The possible implications of the findings for the optimization of strength of reaction-bonded silicon nitride are briefly discussed.     

Microstructure stability of fine-grained silicon carbide ceramics during annealing

Fine-grained silicon carbide ceramics with an average grain size of 140 nm or smaller were prepared by low-temperature hot-pressing of very fine -SiC powders using Al₂O₃-Y₂O₃-CaO (AYC) or Y-Mg-Si-Al-O-N glass (ON) as sintering additives. The microstructure stability of the resulting fine-grained SiC ceramics was investigated by annealing at 1850°C and by evaluating quantitatively the grain growth behavior using image analysis. The phase transformation of SiC in AYC-SiC was responsible for the accelerated abnormal grain growth of platelet-shaped grains. In contrast, the phase transformation in ON-SiC was suppressed, which resulted in a very stable microstructure.     

Preparation of silicon carbide powders by chemical vapour deposition of the SiH4-CH4-H2 system

Chemical vapour deposition (CVD) of the SiH₄ + CH₄ + H₂ system was applied to synthesize-silicon carbide powders in the temperature range 1523 to 1673 K. The powders obtained at 1673 K were single-phase-SiC containing neither free silicon nor free carbon. The powders obtained below 1623 K were composite powders containing free silicon. The carburization ratio (SiC/(SiC + Si)) increased with increasing reaction temperature and total gas flow rate, and with decreasing reactant concentration. The average particle sizes measured by TEM ranged from 46 to 114nm, The particle size increased with the reaction temperature and gas concentration but decreased with gas flow rate. The-SiC particles obtained below 1623 K consisted of a silicon core and a-SiC shell, as opposed to the-SiC particles obtained at 1673 K which were hollow. Infrared absorption peaks were observed at 940 and 810 cm^–1 for particles containing a silicon core; whereas a single peak at about 830 cm^–1 with a shoulder at about 930 cm^–1 was observed for the-SiC hollow particles. The lattice parameter of-SiC having a carburization ratio lower than 70 wt%, was larger than that of bulk-SiC and decreased with the increasing carburization ratio. However, when the carburization ratio exceeded 70 wt%, the lattice parameter became approximately equal to that of bulk-SiC.     

Synthesis of titanium nitride by a spark-discharge method in liquid ammonia

Titanium nitride powders were synthesized by the spark-discharge method in liquid ammonia at — 78 to 130 °C and 3.5–10.5 kV discharge voltage using titanium pellets as the starting materials. Titanium nitride possessing nitrogen defect, TiN_1–x (x0.5), was obtained as the main product, together with small amounts of -Ti alloyed with nitrogen. The increase in temperature of the liquid ammonia resulted in an increase in the titanium nitride content in the product but a decrease in the powder production rate. By calcining the mixed powders of TiN_1–x and -Ti in a nitrogen atmosphere around 1200 °C, stoichiometric TiN was obtained as single phase.     

Conversion of precipitated silica from geothermal water to silicon nitride

Precipitated colloidal silica from geothermal discharge waters of Wairakei, New Zealand was used as the raw material to produce silicon nitride. Mixtures of and forms of silicon nitride in the ratio 90/10 to 95/5 were produced by carbothermal reduction and nitridation of this silica in the temperature range 1350 to 1440° C between 2 and 10h. Three other commercial fine-grained silicas were also nitrided under the same conditions. The geothermal silica was found to be as good if not better than any of these silicas.     

Factors influencing the crystallization of ultrafine plasma-synthesized silicon nitride as a single powder and in composite SiC-Si3N4 powder

A study of various parameters affecting the crystallization process of amorphous silicon nitride produced by plasma gas-phase reaction was undertaken to determine the conditions under which whiskers are formed. This process is influenced by the ammonium chloride content of the starting powder and the presence of nitrogen in the furnace atmosphere. This last parameter is also influential on the / phase ratio, along with other factors like the silica content, temperature and duration of the thermal treatment. Heat treatment at 1500°C for 30 min under argon produced well-defined -Si₃N₄ crystals with a hexagonal cross section, a mean length around 0.8 m, and no sign of agglomeration. Under the same conditions, crystallization of silicon nitride in SiC-Si₃N₄ composite did not give crystals, but Si₃N₄ whiskers. Therefore silicon carbide plays a major role in their formation.     

The α- to β-Si3N4 transformation in the presence of liquid silicon

The compacts consisted of , -Si₃N₄ and free silicon are heat treated in the range 1650° C to 1750° C in an argon atmosphere in order to observe the following behaviours; the to phase transformation and variations of the microstructure during heat treatment in silicon nitride. For the microstructural observation of the heat treated specimens, the same grains in the polished surface were investigated before and after eliminating the retained silicon by etching. The to phase transformation, in this case, occurs via silicon melts irrespective of added -Si₃N₄. Both and phases are soluted and precipitated into molten silicon and their morphology are changed from an equiaxed shape to prismatic one. Although elongated grains are precipitated at low temperature or in the early stage of heat treatment, fine precipitated grains are mainly observed with increasing heat treating temperature.     

Synthesis and characterization of silicon nitride whiskers

Silicon nitride whiskers were synthesized by the carbothermal reduction of silica under nitrogen gas flow. The formation of silicon nitride whiskers occurs through a gas-phase reaction, 3SiO(g)+3CO(g)+2N₂(g)=Si₃N₄()+3CO₂(g), and the VS mechanism. The generation of SiO gas was enhanced by the application of a halide bath. Various nitrogen flow rates resulted in different whisker yields and morphologies. A suitable gas composition range of N₂, SiO and O₂ is necessary to make silicon nitride stable and grow in a whisker form. The oxygen partial pressure of the gas phase was measured by an oxygen sensor and the gas phase was analysed for CO/CO₂ by gas chromatography. Silicon nitride was first formed as a granule, typically a polycrystalline, and then grown as a single crystal whisker from the {1 0 0} plane of the granule along the 210 direction. The whiskers were identified as-sialon with Z value ranging from 0.8 to 1.1, determined by lattice parameter measurements.