Sihcon nitride

SiHcon nitride (see Nitrides) is a key material for stmctural ceramic appHcations in environments of high mechanical and thermal stress such as in vehicular propulsion engines. Properties which make this material uniquely suitable are high mechanical strength at room and elevated temperatures, good oxidation and creep resistance at high temperatures, high thermal shock resistance, exceUent abrasion and corrosion resistance, low density, and, consequently, a low moment of inertia. Additionally, siHcon nitride is made from abundant raw materials. 

Properties. Properties of stmctural siHcon nitride ceramics are given in Table 2. These values represent available, weU-tested materials. However, test methodology and the quaHty of the specimens, particularly their surface finish, can affect the measured values. Another important material property is tensile strength. Values obtained on Norton s NT154 material are 750 MPa at RT, 500 MPa at 1200°C, and 350 MPa (50,000 psi) at 1400°C (62). 

In other useful appHcations, siHcon nitride bearings have been found to offer exceUent performance siHcon nitride cutting tool inserts are a commercial product wear parts such as sand blast nozzles, seals, and die liners are also commercially produced the superior performance of heat exchangers has been demonstrated and there are also military appHcations. 

Exposure limits for siHcon carbide and powders of zirconium compounds (including zirconium dioxide) have been estabHshed by ACGIH. TLV—TWA s are 10 mg/m and 5 mg/m, respectively. OSHA guidelines for zirconium compounds call for a PEL of 5 mg/m. There are no exposure limits for siHcon nitride powder, but pmdent practice suggests a TLV—TWA of 0.1 mg/m. The soHd ceramics present no apparent health hazard. In machining such ceramics, however, care should be taken to prevent inhalation of respirable particles in amounts in excess of estabHshed limits. Disposal should be in approved landfills the materials are inert and should pose no danger to the environment. 

Sihcon nitride can be heated ia air up to 1450—1550°C. In nitrogen, inert gas, or reducing atmosphere, Si N can be heated up to 1750°C. Above 1750°C, decomposition and sublimating evaporation become severe. When in the presence of carbon, however, Si N stabiUty depends on temperature and pressure. The equiUbrium temperature for the reaction... 

Sihcon nitride occurs in two forms, a-Si N and P-Si N. Pure Si N is white, but the colors of commercial materials may be tan, gray, or black because of residual siUcon or impurities. Si N may be prepared by nitriding siUcon powder at 1200—1400°C or, for extremely fine-grained Si N, by the reaction of SiCl or SiH and N2 or NH (see also Advanced ceramics). 

Fig. 2. Flow sheet for the manufacture of self-bonded, reaction-sintered sihcon nitride. Courtesy of Annawerk, Ceranox (Roedental, Germany).

Annual production of sihcon nitride is ca 100—200 t. Utility-grade sihcon nitride costs 4—5/kg in 100- to 500-kg quantities. The reaction-sintered parts are sold for 120 to 300/kg, depending on complexity of shape. Hot-pressed, fully dense Si N parts are priced 5—10 times higher than reaction-sintered parts. 

Sihcon nitride is one of the few nonmetaUic nitrides that is able to form alloys with other refractory compounds. Numerous soHd solutions of P-Si N and AI2O2 have gained technical interest. Many companies have begun to mass produce reaction-sintered and hot-pressed Si N parts. 

Sihcon nitride has good strength retention at high temperature and is the most oxidation resistant nitride. Boron nitride [10043-11 -5] has excellent thermal shock resistance and is in many ways similar to graphite, except that it is not an electrical conductor. 

Figure 4 shows the basic constmetion of the devices used in different appHcations, involving the deposition of multilayers of i -SiH of intrinsic (/), doped ), and closely aUied films, such as amorphous siHcon nitride, SiN, and transparent conducting oxide (TCO). As in crystalline... 

Besides the chemical industry, sihcon is used as a powder in the ceramics (qv) industry for the production of sihcon carbide and sihcon nitride parts (see Advanced ceramics). Sihcon powder is also used as an explosive for defense apphcations and in the refractory industry for plasma spraying with other oxide mixtures (see Refractory coatings). 

The analogous reaction with ammonia leads ultimately to sihcon nitride. In the past, hydrocarbon soluble fractions of the ammonolysis were iacorrecdy referred to as sihcon diimide. This improper designation occasionally persists as of the mid-1990s. 

Sihcon carbide is comparatively stable. The only violent reaction occurs when SiC is heated with a mixture of potassium dichromate and lead chromate. Chemical reactions do, however, take place between sihcon carbide and a variety of compounds at relatively high temperatures. Sodium sihcate attacks SiC above 1300°C, and SiC reacts with calcium and magnesium oxides above 1000°C and with copper oxide at 800°C to form the metal sihcide. Sihcon carbide decomposes in fused alkahes such as potassium chromate or sodium chromate and in fused borax or cryohte, and reacts with carbon dioxide, hydrogen, ak, and steam. Sihcon carbide, resistant to chlorine below 700°C, reacts to form carbon and sihcon tetrachloride at high temperature. SiC dissociates in molten kon and the sihcon reacts with oxides present in the melt, a reaction of use in the metallurgy of kon and steel (qv). The dense, self-bonded type of SiC has good resistance to aluminum up to about 800°C, to bismuth and zinc at 600°C, and to tin up to 400°C a new sihcon nitride-bonded type exhibits improved resistance to cryohte. 

Materials made of siHcon nitride, siHcon oxynitride, or sialon-bonded siHcon carbide have high thermal shock and corrosion resistance and may be used for pump parts, acid spray nozzles, and in aluminum reduction ceUs (156—159). A very porous siHcon carbide foam has been considered for surface combustion burner plates and filter media. It can also be used as a substrate carrying materials such as boron nitride as planar diffusion source for semiconductor doping appHcations. 

---